Controlled release dual walled microcapsules

ABSTRACT

A method of forming dual melamine/acrylic walled microcapsules having improved physical properties and release control as well as the microcapsules formed by the process wherein the capsule wall is formed by the use of select (meth)acrylate monomers and/or oligomers and/or select self-condensing melamine resins.

RELATED APPLICATIONS

The present application is a divisional application of U.S. patentapplication Ser. No. 14/884,684 filed Oct. 15, 2015 which claims thebenefit of prior filed U.S. Provisional Application No. 62/064,906 filedOct. 16, 2014 entitled “Controlled Release Microcapsules”; U.S.Provisional Application No. 62/117,604 filed Feb. 18, 2015 entitled“Controlled Release Dual Walled Microcapsules”; and U.S. ProvisionalApplication No. 62/199,340 filed Jul. 31, 2015 entitled “High StrengthMicrocapsules”, the contents of all of which are hereby incorporatedherein in their entirety by reference.

FIELD OF THE INVENTION

The present disclosure relates to improved dual melamineresin/-(meth)acrylate polymer walled microcapsules wherein theimprovement comprises the use of select combinations of (meth)acrylateesters as the building blocks of the (meth)acrylate polymer. The presentdisclosure also relates to an improved method for the production of dualmelamine resin/-(meth)acrylate polymer walled microcapsules wherein theimprovement comprises the use of select combinations of (meth)acrylateesters in the production of the microcapsules. The present disclosurealso relates to an improved method for the production of dual melamineresin/(meth)acrylate polymer walled microcapsules and the microcapsulesso formed wherein the improvement comprises the use of selectcombinations of (meth)acrylate esters in the production of themicrocapsules together with the concurrent, as opposed to sequential,polymerization of the (meth)acrylate ester and melamine resin in theformation of the microcapsule wall. Finally, in yet another aspect, thepresent invention relates to an improved method for the production ofdual melamine resin/(meth)acrylate polymer walled microcapsules and themicrocapsules so formed wherein the improvement comprises the use ofselect melamine resin prepolymers and/or polymers and/or theirprecursors, which are capable of self-condensation.

In addition, the present teachings are related to and an extension ofthose disclosed in U.S. Provisional Patent Application No. 62/064,906filed on Oct. 16, 2014, the contents of which are hereby incorporated byreference. Specifically, the oil phase (meth)acrylate monomers,oligomers and/or prepolymers and the water phase (meth)acrylatemonomers, oligomers and prepolymers disclosed and employed herein arealso disclosed and employed in the prior filed provisional application.Accordingly, their relative constituents and make-up (e.g., ratio ofmonomers/oligomers) as well as the general amounts by which each is usedin forming their respective component, all as described herein andtherein, are equally applicable to the teachings of this application aswell as the aforementioned Provisional Application.

BACKGROUND

Microcapsules and microencapsulation technology are old and well knownand their commercial applications varied: Microcapsules have played asignificant role in various print technologies where a paper or otherlike substrate is coated with microcapsules containing ink or anink-forming or inducing ingredient which microcapsules release theingredient, generating an image, when fractured by pressure, as by aprinting press or a stylus. Microcapsules have also played a significantrole in various adhesive and sealant technologies including theencapsulation of solvents for solvent swellable/tackified preappliedadhesives whereby fracture of the microcapsules releases the solventwhich softens or tackifies the adhesive to enable bonding and whichre-hardened upon evaporation of the solvent. In other adhesive andsealant applications, the microcapsules contain one or more componentsof a curable or polymerizable adhesive or sealant composition which,upon release, leads to the cure or polymerization of the adhesive orsealant. In all of these early applications, functionality and efficacy,especially for long term storage and utility, is dependent upon theintegrity of the microcapsule walls where the sought after integritypertains to both strength, so as to avoid premature fracture, as well asimpermeability, so as to prevent leakage and/or passage of the contentsof the microcapsule through the microcapsule walls. In the formersituation, parts having a preapplied microencapsulated adhesive have atendency to bond together if they hit one another or are stacked uponone another where the pressure of the stack is sufficiently high. Evenif not bonded, the fracture of the microcapsules results in lessadhesive to effect the bond when the bond is intended. Similarly, if themicrocapsule walls allow permeation of the active components through thecell wall, even a slow permeation, the product is short lived as curewill be effected when not intended.

As with most any technology, evolution of microencapsulation technologyhas led to many new applications, including applications that requirechanges in the physical properties of the microcapsules, especiallytheir walls. New applications require microcapsules that fracture morereadily, with less pressure, but not prematurely. Other applicationsrequire microcapsules that specifically allow for a controlled, slowrelease or permeation of the contents from within the microcapsuleswithout the need to actually fracture the same. For example, perfumecontaining microcapsules are oftentimes applied to advertising insertsin magazines so that the reader can sample the smell of the perfume.Here strength is needed to avoid premature fracturing of themicrocapsules due to the weight and handling of the magazine; yet, themicrocapsules need ease of fracture so that the reader can simplyscratch the treated area to release the contents of the microcapsule. Atthe same time, it is desirable to allow for some release of thecontents, even without fracturing, to induce the reader to want toscratch the sample to get a more accurate sense of the smell.

Another application for microcapsules is in laundering and fabrictreatments. A number of products exist wherein microcapsules of variousingredients, including perfumes, are applied to strips of a fabricmaterial and added to the dryer wherein the tumbling action and/or heatof the dryer causes the microcapsules to fracture, releasing theingredients which, in a volatilized state, permeate and deposit upon thecontents of the dryer. This methodology applies that “fresh out of thedryer” smell, but is short lived as the perfume continues to volatilizefrom the treated fabric. Other products exist whereby microcapsulescontaining perfumes and other ingredients are applied directly orindirectly to the fabric, especially apparel, to provide a longer livedfreshness to the same. Here, the performance or efficacy of theseproducts is oftentimes short lived as the content of the microcapsulesescapes too readily from the microcapsules and/or the walls of themicrocapsules are too weak and/or have too little give such that normalwearing of the fabric causes the microcapsules to break too readily.Opportunities abound for new microcapsules that address the specificrequirements of a given application as well as microcapsules that offerbetter performance and properties than are attainable with current stateof the art microcapsule technology.

Whether applications have driven the evolution of microcapsuletechnology or the evolution of microcapsule technology has driven theirexpanded applications, or perhaps a little of both, there has been andcontinues to be constant development in microencapsulation technology,both in terms of their production/process methodology and theirchemistry. Early melamine formaldehyde microcapsules continue to evolve;yet concurrently, they have, to some extent, given way to acrylic andother microcapsule chemistries and technologies. In turn, both havecontinued to evolve further to dual walled microcapsules of eachchemistry as well as both chemistries. While the basic building blocksof the capsule walls have largely remained the same, the specificselection of building blocks and methodology has led to newer andimproved microcapsules enabling the microencapsulation of a broaderarray of ingredients, compounds and elements.

Despite all the advances and improvements, there is still a need forimproved specialty microcapsules that provide a suitable mix ofrelease/permeability characteristics and physical properties for today'sdemanding applications. This is especially so in the area of perfumesand other odiferous ingredients, particularly in relation to fabric,textile and garment treatment, where controlled release and longevity aswell as capsule strength and integrity are necessary.

SUMMARY OF THE INVENTION

According to the present teachings there are provided novel, improvedmicrocapsules and methods of forming the same, which exhibit markedimprovement in release characteristics and/or excellent physicalproperties and attributes, preferably attributes of both.

According to a first embodiment of the present teachings there isprovided improved dual melamine resin/(meth)acrylate polymer walledmicrocapsules wherein the improvement comprises the use of a combinationof (a) at least one oil soluble or dispersible amine (meth)acrylate, (b)at least one oil soluble or dispersible acidic (meth)acrylate or atleast one oil soluble or dispersible simple acid or both, and (c) atleast one oil soluble or dispersible multifunctional (meth)acrylatemonomer or oligomer in forming the (meth)acrylate ester-based portion ofthe microcapsule wall.

According to a second embodiment there is provided an improved method ofmaking dual melamine resin/(meth)acrylate polymer walled microcapsuleswherein the improvement comprises the use of a combination of (a) atleast one oil soluble or dispersible acidic (meth)acrylate, (b) at leastone oil soluble or dispersible simple base, and (c) at least one oilsoluble or dispersible multifunctional (meth)acrylate monomer oroligomer in forming the (meth)acrylate ester-based portion of themicrocapsule wall.

According to a third embodiment there is provided an improved oil/waterphase method of making dual melamine resin/(meth)acrylate polymer walledmicrocapsules and the microcapsules so formed wherein the improvementcomprises (i) the use of either (A) (a) at least one oil soluble ordispersible amine (meth)acrylate, (b) at least one oil soluble ordispersible acidic (meth)acrylate or at least one oil soluble ordispersible simple acid or both, and (c) at least one oil soluble ordispersible multifunctional (meth)acrylate monomer or oligomer or (B) acombination of (a) at least one oil soluble or dispersible acidic(meth)acrylate, (b) at least one oil soluble or dispersible simple base,and (c) at least one oil soluble or dispersible multifunctional(meth)acrylate monomer or oligomer in forming the (meth)acrylateester-based portion of the microcapsule wall and (ii) the concurrent ornear concurrent deposition and polymerization of the (meth)acrylatepolymer and melamine resin at the oil/water phase interface.

According to a fourth embodiment there is provided an improved method ofmaking dual melamine resin/(meth)acrylate polymer walled microcapsulesand the microcapsules so formed wherein the improvement comprises theuse of (a) at least one water soluble or dispersible multifunctional(meth)acrylate monomer or oligomer alone or in combination with (b) atleast one water soluble or dispersible mono- and/or di-functional(meth)acrylate and/or (c) at least one water soluble or dispersiblesimple base in the production of the (meth)acrylate ester-based portionof the microcapsule wall.

Finally, according to a fifth embodiment there is provided an improvedmethod of making dual melamine resin/(meth)acrylate polymer walledmicrocapsules and the microcapsules so formed wherein the improvementcomprises the select use of water soluble or dispersible melamine resinprepolymers and/or polymers and/or the precursors therefore which areable to polymerize/copolymerize through self-condensation. This fifthembodiment is especially applicable when applied to each of theforegoing four embodiments.

While the recitation of the first through fourth embodiments aboveteaches the use of the combination of the therein mentioned(meth)acrylate ester monomers and/or oligomers, it is also to beappreciated that one may also or in substitution therefor employ apreformed oligomer/prepolymer of the select (meth)acrylate estermonomers and/or oligomers. Specifically, e.g., one may employ anoligomer/prepolymer comprising the reaction product of (a) at least oneoil soluble or dispersible amine (meth)acrylate, (b) at least one oilsoluble or dispersible acidic (meth)acrylate or at least one oil solubleor dispersible simple acid or both, and (c) at least one oil soluble ordispersible multifunctional (meth)acrylate monomer or oligomer, with orwithout isolation and/or purification thereof as the wall formingcomponent. Alternatively, one may form oligomers of two or all three ofthe (meth)acrylate esters and/or oligomers (a), (b) and (c) and add thethird or additional monomer and/or oligomer, respectively, during thewall forming stage.

The “dual walled” microcapsules produced according to the presentteaching are such that one of the innermost shell portion and theoutermost shell portion of the microcapsule wall is essentiallyhomopolymers or, as appropriate copolymers of the wall forming materialsof the respective wall forming composition, e.g., a melamine polymer inthe case of the melamine based wall forming composition or a(meth)acrylic polymer in the case of the (meth)acrylate based wallforming composition: which is which will depend upon the specific stepsand sequence of steps employed. In contrast, the intermediate region ofthe shell wall, i.e., that region where the shell wall forming materialsof each come in contact with the other, may present itself in a numberof different states depending upon the specific steps and sequence ofsteps employed and, equally important, the selection of the monomers,oligomers and/or prepolymers of each shell wall forming material used.Specifically, the intermediate region may show a distinct transition ofone composition to the other, as if one layer is built upon the other,or it may manifest in the form of a transition region of varyingthickness where the transition region comprises (a) an interpenetratingnetwork of the two polymers which physically lock the two wall materialstogether, (b) a copolymer of the monomers, oligomers and/or prepolymersof each, or (c) both.

A distinct transition will typically be found where, e.g., onesequentially forms the microcapsule wall, encapsulating the core, withone material and, once that wall is fully formed, depositing andbuilding or polymerizing the second wall forming material upon thealready formed wall. Alternatively, the core composition itself maycomprise the second wall forming material and the outer wall could beformed first on the droplet of the core and inner wall forming materialand then the overall composition subjected to conditions which thenpolymerize the wall forming materials contained within the droplet tobuild the second portion of the wall from within.

Despite the clear sequential build noted in the preceding paragraph, itis also be understood that a transition region may still manifest itselfat the interface of the two polymers, particularly in thosecircumstances where the polymer of the first formed wall has groups thatare reactive with one or more of the monomers or components of thesecond wall forming material and/or where the first formed wall haspolymer chains that extend from the surface thereof and/or voids or aloose network of polymer chains that allow the monomers and oligomers ofthe second wall forming material to penetrate prior to and/or during thepolymerization of the second wall forming material. In the first, wherereactive groups are present, there is a copolymerization creating achemical bond. In the second, where the polymer chains extend from thesurface and/or voids or a loose polymer network is formed, aninterpenetrating network is formed physically locking one wall formingmaterial to the other.

On the other hand, a transition region which may be in the form of aninterpenetrating network of one polymer or wall forming material withthe other and/or a copolymer region is typically, though notnecessarily, formed if one elects to form the shell wall from both shellwall forming materials concurrently or with only a brief delay orstagger in the initiation of polymerization of one and then the other.Most preferably, the polymerization of one shell wall forming materialis initiated and allowed to progress to a point where the core ispartially encapsulated, perhaps twenty-five percent or more, preferablyfifty percent or more, but not fully, encapsulated or, at best, has amonolayer or so of wall formed across the surface of the core materialbefore initiating polymerization of the second wall forming material.Alternatively, one may initiate polymerization of one wall formingmaterial to form a seed microcapsule which has the essential structureof a shell, but is still permeable to monomer and/or initiator orradicals prior to initiation of polymerization of the second wallforming material.

Regardless of which of the foregoing embodiments is followed, once theintermediate or transition region of the shell wall is formed and thewall forming materials of each composition is fully isolated from theother, the polymerization of the shell wall forming materials continues,but is now limited to those components of that shell wall formingcomposition. Where the wall is formed sequentially, only the second wallforming material will continue to polymerize, either on the exteriorsurface or on the interior surface of the shell wall as appropriate.Where the wall forming is concurrent or slightly staggered, both wallforming materials will continue to polymerize, the inner or core wallbuilding material building from within upon the inner surface of theshell wall and the continuous phase or exterior wall forming materialcontinuing to build from without upon the exterior surface of themicrocapsule wall.

The microcapsules and the microencapsulation processes of the presentteachings are applicable to most any application where microcapsules canbe used and are especially suitable for use in those instances wherecontrolled release of the microencapsulated material is desired whileintegrity of the microcapsule wall is maintained. In particular, thepresent microcapsules are especially suited for use where an aromaticingredient is to be encapsulated which ingredient is intended to allowfor the gradual release of the aromatic ingredient or, at least, itsaroma or smell, while withstanding moderate physical forces to themicrocapsules so as to avoid premature and/or undesired rupture of theso formed microcapsules. In particular, the microcapsules of the presentteachings have significant use in scratch-n-sniff applications, inlaundry applications, in odor control applications, etc.

DETAILED DESCRIPTION

As used in the specification and claims, the term (meth)acrylate refersto the acrylate as well as the methacrylate: when just the acrylate isintended to be exemplified, it will be so presented, e.g., isobornylacrylate, and when just the methacrylate is intended to be exemplified,it will be so presented, e.g., isobornyl methacrylate. Hence, isobornyl(meth)acrylate refers to both isobornyl acrylate and isobornylmethacrylate. The use of the phrase “(meth)acrylate oligomer/prepolymer”means that the (meth)acrylate material may exist as an oligomer, as aprepolymer or as a combination of both oligomers and prepolymers, withor without some monomer. Similarly, the phrase “melamine prepolymer”means oligomer, prepolymer or both oligomer and prepolymer of themelamine material, with or without some monomer/precursor materials.Finally, the word “initiator” as used herein is intended to mean trueinitiators, such as the free radical initiators, for inducingpolymerization of the acrylate esters as well as those catalysts and/oraccelerators, including alkaline inducing agents, which promote and/oraccelerate the polymerization of the monomers, oligomers and/orprepolymers, especially the melamine prepolymers and/or precursorstherefore.

Additionally, the descriptors “water soluble or dispersible”, “watersoluble”, and “water dispersible” when referencing certain(meth)acrylate monomers and/or oligomers or initiators means that thespecified component is soluble or dispersible in the given matrixsolution on their own or in the presence of a suitable solubilizer oremulsifier or upon attainment of certain temperatures and/or adjustmentof pH. Furthermore, as presented herein, the microcapsules and theirmethods of production are oftentimes characterized as being “improved.”With respect to the microcapsules themselves, the improvement is withrespect to similar microcapsules formed from some, but not all, of thespecified components. For example, an improved microcapsule formed ofone of the select combinations of (meth)acrylic esters will typicallyshow improved physical characteristics as compared to a single walledmicrocapsule formed from some, but not all, of those (meth)acrylicesters or to a dual walled MF/Acrylic microcapsule formed of melamineresin and, again, some, but not all, of those (meth)acrylic esters. Withrespect to the method, the improvement may be with respect to thephysical characteristics of the so formed microcapsules or with respectto the ease, simplicity, and/or efficacy of the method itself, or both.

According to a first embodiment of the present teachings there isprovided improved dual melamine resin/(meth)acrylate polymer walledmicrocapsules wherein the improvement comprises the use of a combinationof (a) at least one oil soluble or dispersible amine (meth)acrylate, (b)at least one oil soluble or dispersible acidic (meth)acrylate or atleast one oil soluble or dispersible simple acid or both, and (c) atleast one oil soluble or dispersible multifunctional (meth)acrylatemonomer or oligomer in forming the (meth)acrylate ester-based portion ofthe microcapsule wall.

According to a second embodiment there is provided an improved method ofmaking dual melamine resin/(meth)acrylate polymer walled microcapsuleswherein the improvement comprises the use of a combination of (a) atleast one oil soluble or dispersible acidic (meth)acrylate, (b) at leastone oil soluble or dispersible simple base, and (c) at least one oilsoluble or dispersible multifunctional (meth)acrylate monomer oroligomer in forming the (meth)acrylate ester-based portion of themicrocapsule wall.

According to a third embodiment there is provided an improved oil/waterphase method of making dual melamine resin/(meth)acrylate polymer walledmicrocapsules and the microcapsules so formed wherein the improvementcomprises (i) the use of either (A) (a) at least one oil soluble ordispersible amine (meth)acrylate, (b) at least one oil soluble ordispersible acidic (meth)acrylate or at least one oil soluble ordispersible simple acid or both, and (c) at least one oil soluble ordispersible multifunctional (meth)acrylate monomer or oligomer or (B) acombination of (a) at least one oil soluble or dispersible acidic(meth)acrylate, (b) at least one oil soluble or dispersible simple base,and (c) at least one oil soluble or dispersible multifunctional(meth)acrylate monomer or oligomer in forming the (meth)acrylateester-based portion of the microcapsule wall and (ii) the concurrent ornear concurrent deposition and polymerization of the (meth)acrylatepolymer and melamine resin at the oil/water phase interface.

According to a fourth embodiment there is provided an improved method ofmaking dual melamine resin/(meth)acrylate polymer walled microcapsulesand the microcapsules so formed wherein the improvement comprises theuse of (a) at least one water soluble or dispersible multifunctional(meth)acrylate monomer or oligomer alone or in combination with (b) atleast one water soluble or dispersible mono- and/or di-functional(meth)acrylate and/or (c) at least one water soluble or dispersiblesimple base in the production of the (meth)acrylate ester-based portionof the microcapsule wall.

Finally, according to a fifth embodiment there is provided an improvedmethod of making dual melamine resin/(meth)acrylate polymer walledmicrocapsules and the microcapsules so formed wherein the improvementcomprises the select use of water soluble or dispersible melamine resinprepolymers and/or polymers and/or the precursors therefore which areable to copolymerize through self-condensation. This fifth embodiment isespecially applicable when applied to each of the foregoing fourembodiments.

As noted in the background section, microcapsules and microencapsulationprocesses are well known and have been practiced for decades. Exemplarymicrocapsules include those whose microcapsule walls are formed ofmelamine resin, (meth)acrylic polymer, and dual melamineresin/(meth)acrylic polymer. These are described in, among others:Schwantes—U.S. Pat. No. 7,736,695; U.S. Pat. No. 8,071,214 and U.S. Pat.No. 8,455,098; Bodmer et. al. —U.S. Pat. No. 6,544,926; Lee et. al. —US2007/0138673; Sakamoto et. al. —U.S. Pat. No. 5,061,410; Liang et. al.—U.S. Pat. No. 4,977,060 and Bowman—U.S. Pat. No. 4,675,249; all ofwhich are incorporated herein by reference in their entirety. Thoseskilled in the art, having the benefit of the present teachings, willreadily be able to employ said processes and modify said processes topractice the present invention.

The microencapsulation processes of the present teachings are of twogeneral types: a dual oil/aqueous phase system and process and a dualaqueous based system and process. The wall formation from each phase maybe performed concurrently, with a stagger or delay sequentially. Thelatter is more typical of the dual water phase process while the othertwo are more typical of the dual oil/water phase process.

The first microencapsulation process involves the use of a dualoil/water phase system comprising a melamine containing aqueous phaseand a (meth)acrylate ester containing oil phase. While the dualoil/water phase process may be used to form microcapsules having eitheran (meth)acrylic/melamine or melamine/(meth)acrylic core/shellconstruction, it is especially suited, particularly from a conveniencestandpoint, for those processes where the core is an oil phase core andthe inner wall of the microcapsule is a (meth)acrylic polymer wall. Thelatter process generally involves an emulsion or dispersion of the oilphase dispersed in a continuous aqueous phase. In these systems, thediscontinuous phase will typically comprise or contain the core materialto be encapsulated as well as the inner wall forming materials. Thesedual phase systems are especially suited for allowing for a concurrentor staggered/delayed wall formation whereby formation of the shell wallfrom the wall forming material of one phase is initiated and, shortlythereafter, preferably before full encapsulation is attained,polymerization of the second wall forming material is initiated so thatthere is some dual polymerization at the interface of the two phases. Ofcourse, one may opt to employ a sequential process where microcapsulesare formed of one wall forming material and then subjected to a secondwall formation process using the second wall forming material.

The second microencapsulation process generally employs two water phasewall forming compositions; though here, unlike in the dual oil/waterphase process, the shell wall formation from the first water phasecomposition is more typically completed or substantially completedbefore the second water phase composition is added to form the secondshell layer. In this instance, the first of the two water phasecompositions will contain the core material to be encapsulated as wellas the initial wall forming materials.

Having addressed the phases of the encapsulation process attention isnow directed to the processes by which the microcapsules are made. Forconvenience, the discussion of the dual phase system is presented on thebasis of an oil phase core and inner wall forming composition and anaqueous phase material as the continuous phase and the outer wallforming composition.

A first step of the dual phase process is the formation of the oil phasecomposition. Generally speaking, the oil phase composition will compriseeither (A) (a) at least one oil soluble or dispersible amine(meth)acrylate, (b) at least one oil soluble or dispersible acidic(meth)acrylate or at least one oil soluble or dispersible simple acid orboth, and (c) at least one oil soluble or dispersible multifunctional(meth)acrylate monomer or oligomer; (B) a combination of (a) at leastone oil soluble or dispersible acidic (meth)acrylate, (b) at least oneoil soluble or dispersible simple base, and (c) at least one oil solubleor dispersible multifunctional (meth)acrylate monomer or oligomer or (C)a (meth)acrylate oligomer/prepolymer of (A) or (B) and the core materialitself, i.e., the material, ingredient, etc. that is intended to beencapsulated. Most preferably, the oil phase wall forming material is inthe form of the (meth)acrylate oligomer/prepolymer which is pre-formedor formed in-situ as a first pre-step or sub-step to the formation ofthe oil phase.

In the case of the pre-formed (meth)acrylate oligomer/prepolymer, thesame may be purchased or formed and stored for later use as a separateingredient in the microencapsulation processes. However, it is preferredthat the (meth)acrylate oligomer/prepolymer be formed in-situ as a firststep or pre-step in microencapsulation process, with or withoutisolation. This allows for one to make adjustments in the relative ratioof the (a), (b) and (c) components to optimize the (meth)acrylateoligomer/prepolymer for the specific end-use of the microcapsules. Ofcourse, it is also to be understood that while it is preferred that the(meth)acrylate oligomer/prepolymer be formed of all three constituents,(a), (b) and (c), an oligomer/prepolymer may also be formed of any twoof said constituents or from less than the full amount of saidconstituents with the remaining constituent and/or the balance of theremaining constituents added to the oil phase composition as a secondoil phase composition prior to or concurrent with the wall formationstep.

Furthermore, in the case of the in-situ formed (meth)acrylateoligomer/prepolymer, the components therefore are combined together witha suitable carrier or oil phase material, which may be the core material(or in addition to the core material), and subjected to suitableconditions, preferably in the presence of a suitable initiator, and fora sufficient period of time to generate the desired oligomer/prepolymer.The so formed (meth)acrylate oligomer/prepolymer, with or withoutisolation, is then combined with a second oil phase composition which,preferably, contains an initiator and, most likely and preferably, thecore material (or the remaining portion thereof, as appropriate) to beencapsulated and, optionally, an acid or other ingredient that willfacilitate or drive the oligomer/prepolymer to the interface of the oilphase and the water phase. Though the foregoing teaches the formation ofthe (meth)acrylate oligomer/-prepolymer prior to adding the remainingoil phase composition components, it is also to be appreciated that allor most all of the components of the oil phase composition can becombined prior to effecting the oligomerization/pre-polymerization ofthe monomers/oligomers to produce the (meth)acrylateoligomer/prepolymer.

In any event, once the oil phase composition is formed and, preferably,the (meth)acrylate oligomer/prepolymer formed as well, the resultant oilphase composition is then combined with an excess, by volume, of a firstwater phase composition which preferably comprises a non-ionicemulsifier and/or an initiator, which may be the same or a differentinitiator than is present in the oil phase composition, or a combinationof initiators, one of which may be the same as the initiator in the oilphase composition, or a second initiator suitable for effectingpolymerization of the oil phase wall forming material. Optionally, thefirst water phase may also contain water phase wall forming material,monomer and/or initiator for the water phase wall forming material, aswell. The combination of the oil phase and the water phase compositionis then subjected to emulsification/high shear mixing to create adispersion/emulsion of the oil phase in the water phase. Emulsificationis continued until the desired size of the droplets is attained.Although this may vary from application to application, for manyapplications it is desirable that the target droplet size is from 0.1 to80 microns, preferably from 0.5 to 50 microns, more preferably from 1 to30 microns. Larger sizes for particular applications are also feasible.

Following completion of the formation of the emulsion, a second waterphase composition comprising the melamine resin or resin precursors and,as appropriate, suitable initiators and the like is added to the aqueouscontinuous phase with continued mixing. Generally, and preferably, atthis point the high speed shear mixing or milling is stopped and aslower mixing, with or without the switching of the blade element, ismaintained. For example, one may opt to replace theemulsification/milling blade with a mixer blade to maintain a less shearforce mixing of the emulsion.

Notwithstanding the foregoing, it is also be appreciated that one canemploy a single aqueous phase composition which includes all of thenecessary components or ingredients instead of multiple aqueous phasecompositions or the second aqueous phase composition may be added to themixture prior to completion of the emulsification process. However, ineach of these instances, one is merely adding additional volume to thewater phase and the overall composition which reduces the efficiency ofthe emulsification process. Hence, it is preferred that a second waterphase composition be employed and added after completion of theemulsification process.

Concurrent with or following the emulsification of the combined phases,preferably, at a point near or following achievement of the desireddroplet size, the overall reaction mix is subjected to such conditionsas will initiate polymerization of the oil phase wall forming materialsor components in the emulsified droplets so as to commence wallformation at the oil phase/water phase interface. Again, this may be thepolymerization of the initial monomers/oligomers or, most preferably, ofthe (meth)acrylate oligomer/prepolymer. At this point, it may bedesirable to add, if not already present in one or both of the oil andwater phases, an acid or other component that drives or causes thepolymerizable or wall forming materials of each phase to migrate to theoil phase/water phase interface.

Regardless once or shortly after the second water phase compositions isadded to the mix, the composition is then subjected to such conditionsas will activate the initiator and/or initiate or promote thepolymerization of the wall forming material in the continuous phase,i.e., the melamine, while maintaining if not enhancing thepolymerization of the wall forming material in the core. Owing to thenature of the monomers/oligomers, those in the continuous phase willpreferably have a tendency to migrate through the continuous phase tothe oil phase/water phase interface where they deposit and polymerize onthe capsule wall material that is polymerizing out of the oil phase orcore materials. Here, as with the oil phase material, it is contemplatedthat the continuous phase composition includes or has added thereto aningredient or is subjected to conditions which drive the wall formingmaterials therein to the interface.

Once the oil phase droplet is completely encapsulated, capsule wallformation continues until the desired end-point with the oil phase wallforming material continuing to build from the inner surface of thecapsule wall inwards and the continuous phase wall forming material,i.e., the melamine resin, continuing to build and add to the exteriorsurface of the capsule wall. In this way, regardless of what polymers,copolymers, and/or interpolymers (e.g., interpenetrating networks) existin the midsection of the capsule wall, i.e., at the original oil/waterinterface, the inner wall surface and the exterior wall surface of thefinal microcapsules are generally comprised of polymers formed of onlythe oil phase wall forming materials and the aqueous phase wall formingmaterials, respectively.

Further, while the foregoing teaches the initiation of the oil phasewall concurrent with or staggered relative to the polymerization of theaqueous phase melamine resin wall forming material, it is alsocontemplated that the oil phase materials could be fully polymerizedbefore the addition of the second water phase and/or before activationor initiation of the polymerization of the water phase polymerizablematerial. Alternatively, one may also initiate polymerization of theaqueous phase materials before initiation of the oil phase material sothat the oil phase droplet is partially or fully encapsulated with themelamine resin before the oil phase wall forming material begins tobuild upon the inner surface of the melamine resin wall. Mostpreferably, as noted above, the process involves the polymerization ofthe oil phase wall forming material and partial encapsulation of the oilphase droplet therewith prior to initiation of the polymerization of theaqueous phase wall forming material. Alternatively, as noted above, theoil phase may be fully encapsulated in a seed microcapsule, one whosewall completely surrounds the oil droplet but is not integral, rather ithas voids and gaps whereby the liquid/liquid interface between the twophases still exists. In any event, depending upon the selection of thewater phase wall forming materials and the oil phase wall formingmaterials and the timing of their combination, it is contemplated thatthe wall forming component(s) of one may copolymerize with one or moreof the wall forming component(s) of the other and/or form aninterpenetrating network therewith.

The conditions and duration of the curing or polymerization process willvary depending upon the ingredients, most especially the initiators,activators and/or catalysts used, and the desired outcome relative tothe capsule size and, more pertinently, the wall thickness. In the caseof heat activated initiators, it is especially desirable to employactivators that have different activation temperatures and/or havevaried half-lives so that one can better control the extent or degree ofpolymerization. In this regard, the nature of the activation energyemployed, the extent of the exposure to the activation energy, and theduration thereof all have a significant impact on the extent or degreeof cure. In the case of heat activated free radical initiators,generally the higher the temperature to which the activator is exposedabove the activation temperature the more and/or faster free radicalsare generated. Similarly, in the case of actinic radiation activatedfree radical initiators, the higher the intensity of the radiation ofthe requisite wavelength, the greater the effect. Thus, those skilled inthe art having the benefit of the present teachings combined with someexperience with the present process will be able to determine theoperating conditions for best effecting the present encapsulationprocess. Nevertheless, it is also to be appreciated that when combiningtwo or more of the same phase compositions to the other, e.g., thecombination of two water phase compositions or two oil phasecompositions, it is desirable to provide proper mixing to ensure ahomogeneous or near homogeneous mixture before initiatingpolymerization. Similarly, when combining one phase type to the other,it is desirable to ensure that the proper droplet size is attainedbefore initiating polymerization.

From the foregoing, it is apparent that the oil/water phase system andprocess provides for a number of variables. For the sake of providingadditional clarity, one may consider, for example, that in endeavoringto produce about 600 grams of microcapsules one would employ an overallsystem having 10 to 70 weight percent, preferably 35 to 65 weightpercent, oil phase solvent and oil or other core material to beencapsulated; 10 to 70 weight percent, preferably 35 to 65 weightpercent water; and 1 to 40 weight percent, usually 3 to 35 weightpercent, preferably 5 to 30 weight percent of wall forming material. Asto the wall forming materials themselves, the oil phasemonomers/oligomers are generally used in an amount of 10-90, preferably30-80, more preferably, 40-70, most preferably, 55-65 weight percent andthe water phase monomers/resins are employed in an amount of 10-90,preferably, 20-70, more preferably, 30-60, most preferably 35-45 weightpercent, the weight percent based upon the combined weight of the oilphase and water phase wall forming materials.

Though the foregoing amounts are typical, it is also to be understoodthat the use of higher water content levels are possible, but notnecessary and merely creates a dilute solution and/or requires thepresence of higher amounts of the necessary ingredients to provide foran efficacious process. Similarly, higher concentrations of the oilphase materials may be used, but then the concentration of the dropletsbecomes too dense and may result in an unstable emulsion and/orcoalescence of the droplets, or worse, an inversion whereby the oilphase becomes the continuous phase. Regardless, the amount of wallforming material is, in part, a function of the size of themicrocapsules and the properties, especially the physical properties, ofthe resultant microcapsules. Generally, though, the capsule wallcomprises from 1 to 40 weight percent, preferably from 5 to 30 weightpercent, most preferably from 8 to 20 weight percent of themicrocapsule.

The foregoing presents a general overview of the process and alternatesteps that may be used in forming the presently claimed microcapsules inan oil and water system. As noted above, those skilled in the art,having the advantage of the teachings herein, will readily recognizevarious methodologies and process steps, sequences and conditions thatmay be employed or altered to form the microcapsules intended by thepresent teachings. As further exemplification and for the sake of addedclarity, the following paragraphs will present one specific method offorming a (meth)acrylic/melamine dual walled microcapsule having an oilcore with an acrylic inner shell layer employing a first and second oilphase, the first comprising the wall forming materials and the secondthe core material, and a first and second water phase, the firstcomprising emulsifier and/or initiator and the second the melamineresin. Ranges of the reaction parameters are set forth in parenthesis.

An oil/water phase acrylic/melamine dual walled microcapsule is producedas follows:

(I) the components of a first oil phase composition comprising a scentedoil to be encapsulated as the core material and one or more free radicalinitiators are placed in a reactor vessel and mixed at 35° C. under a N₂blanket at a low mixer speed (120 rpm). The mixture is heated over aperiod of about 45 minutes to 70° C. and held at that temperature for anadditional 45 minutes. Thereafter, the mixture is cooled to 50° C. (50°C.-60° C.) over a period of 30 minutes (30-75 minutes) and held at thattemperature.

(II) independently, a second oil phase composition comprising the oilphase wall forming materials is prepared in a separate mixing vessel andheated to 50° C. (50° C.-60° C.) and mixed.

(III) independently a first water phase composition comprising water, aplurality of initiators, one for effecting polymerization of the oilphase wall forming materials and the other for effecting polymerizationof the melamine resin water phase wall forming materials, an emulsifierand a pH adjuster is likewise combined in a separate mixing vessel andheated to 50° C. (50° C.-60° C.) and mixed.

(IV) the second oil phase composition is then added to the reactorvessel containing the first oil phase and the mixture mixed at slowspeed for 10 minutes.

(V) promptly thereafter, the first water phase composition is thengradually added to the reactor vessel containing the combined oil phasematerials under high shear mixing at about 1200 rpm and millingcontinued until the desired droplet size is attained, approximately 60minutes or so. During the milling process, samples of the emulsion areperiodically taken from the reactor vessel to check droplet size. Oncethe desired droplet size is attained, the mixing is stopped and themilling blade replaced with a mixing blade.

(VI) a second water phase composition comprising the water phasemelamine resin wall forming materials, which had been previously mixedand heated to 50° C. (50° C.-60° C.), is then added to the reactionvessel containing the emulsion and the whole of the mixture mixed at lowspeed, ˜120 rpm while elevating the temperature of the mixture to 75° C.over a period of 60 minutes (60-180) with mixing and held for 4 hours.

(VIII) the mixture is then further elevated to 95° C. over a period of60 minutes and held for an additional 6 hours to form the finalmicrocapsules.

It is believed that the initial heating of the first oil phasecomposition in Step (I) initiates the free radical initiator, therebygenerating free radicals which, when the second oil phase composition isadded will enable oligomerization/prepolymerization of the oil phasewall forming materials to form the (meth)acrylate oligomer/prepolymer.Similarly, it is believed that the period of heating and mixingfollowing the addition of the water phase material for formation of theemulsion initiates wall. formation from the oil phase at the interfaceof the oil phase and water phase. Adding the second water phasecomposition shortly thereafter ensures the concurrent polymerization ofthe two wall forming materials at the interface so as to produce theaforementioned interpenetrating network and/or copolymerization.

Of course a multitude of variations in the steps, their sequence, etc.,as well as the introduction of other constituents for aiding and/orfacilitating cell wall formation are also contemplated and can beemployed without diverging from the inventive aspects of the presentteachings. For example, as noted previously, instead of forming the(meth)acrylate oligomer/prepolymer as a step in the process, one mayalso use a preformed (meth)acrylate oligomer/prepolymer. The same alsoholds true for the melamine prepolymer where the prepolymer may beformed as part of the overall process steps or it may be preformed andused in the process, again with or without separation, purificationand/or isolation.

Additionally, the claimed processes may include various additives andother constituents to enable and/or facilitate the formation of themicrocapsules. For example, it is desirable and, at times, necessary, toemploy emulsifiers to aid in the formation and/or stability of the oilin water and/or water in oil dispersions, as appropriate, as well asemulsifiers and/or solubilizers to assist in dispersing and/orsolubilizing the components in their respective phases, i.e., aqueousphase components in the water or aqueous phase matrix material and theoil phase components in the oil phase matrix material. Suitableemulsifiers may be in either or both phases and/or in each, some, or allof the respective premix components of each, e.g., the first water phasecomposition, the second water phase composition, the first oil phasecomposition, the second oil phase composition, etc. Most especially, thematrix phase composition will have an emulsifier for creating anemulsion or droplets of the dispersed phase composition in the matrixphase composition.

Sequencing of the process steps and/or the timing of the same is alsoable to be changed. In each of the foregoing embodiments the core phaseis added to and dispersed in a first matrix phase composition containingone or more initiators for effecting polymerization of one or both wallforming materials. As an alternative, the core phase can be dispersed ina first matrix phase composition which includes the melamine resin wallforming material, or the precursors therefore, but not the initiatortherefore. Similarly, the oil phase, while described above as comprisingthe combination of two separate oil phase compositions, could be made asa single composition or could be the combination of more than twopre-mix compositions. For example, if solubility and/or dispensabilityof the constituents of the oil phase composition is an issue, each canbe separately dissolved/dispersed and then these premixes combined. Thesame also holds true for the water phase which may be formed as a singlecomposition or can be formed in the course of the microencapsulationprocess through the sequential addition of multiple water phase premixesof the components therefore.

Additionally, while the foregoing contemplates a brief delay in theinitiation/polymerization of the wall forming materials of each phase,each may be initiated concurrently or sequentially where a shell or, asnoted above, a seed microcapsule is formed of one of the wall formingmaterials and, once that formation is completed or nearly so, the otheris initiated to build upon the first formed shell wall or at any pointin between. Preferably the initiation of the polymerization of the twowall forming materials is staggered, though just briefly. Mostpreferably, polymerization of the core phase wall forming material isinitiated prior to initiation of the polymerization of the matrix phasewall forming. In any event, where there is a stagger, it is preferredthat it be brief such that the dispersed droplet is not fullyencapsulated by one wall forming material prior to initiation ofpolymerization of the other wall forming material, or if fullyencapsulated, is very thin so as to allow some physical integration ofthe polymer chains of one with the polymer chains of the other asopposed to simply one polymer overlaying or coating the other.Staggering of the initiation/polymerization of the wall formingmaterials may be achieved by, e.g., not adding the matrix phase wallforming materials until after initiating polymerization of the corephase wall forming material; not adding the initiator for thepolymerization of the matrix phase wall forming material until afterinitiating polymerization of the core phase wall forming material,subjecting the reaction mix to conditions which will effectpolymerization of either the core or the matrix wall forming materialbut not the other, etc. Again, a highly desirable objective is to ensurethat the wall forming materials, at least during the initial stages ofcapsule wall formation, engage in some copolymerization and/or form aninterpenetrating network and/or involves a physical entrapment of thepolymer chains of one in the other.

In any event, once the core phase droplet is completely encapsulated,capsule wall formation continues until the desired end-point with thecore phase wall forming material continuing to build from the innersurface of the capsule wall inwards and the matrix phase wall formingmaterial continuing to build and add to the exterior surface of thecapsule wall. In this way, regardless of what polymers, copolymers,and/or interpolymers (e.g., interpenetrating networks) exist in themidsection or body of the capsule wall, the inner wall surface and theexterior wall surface are generally comprised of wholly polymerized coreand matrix phase wall forming materials, respectively.

As noted, oligomerization/prepolymerization and polymerization areinitiated by suitable initiators, most especially, in the case of the(meth)acrylate monomers, oligomers and prepolymers, free radicalinitiators. The specific selection of the initiators is dependent, inpart, upon the monomers, oligomers and/or prepolymers to be polymerizedor further oligomerized as well as the method by which the initiator isactivated: in the case of free radical initiators, the method by whichthe free radical is to be generated, e.g., heat, actinic radiation, etc.Latent initiators are also contemplated where a first action,particularly a chemical reaction, is needed to transform the latentinitiator into an active initiator which subsequently initiatespolymerization upon exposure to polymerizing conditions. Where multipleinitiators are present, it is contemplated, and preferred, that eachinitiator be initiated or suitably initiated by a different condition.For example, each initiator may be initiated by a different temperatureor one may be induced by heat and the other by actinic radiation. Theuse of different initiators with different activation triggers allowsfor more control in the capsule wall formation. Depending upon themethod of activation, control of oligomerization/prepolymerizationand/or wall formation may also be exercised by limiting the time and/orextent of activation, e.g., by exposing the specific reaction mix tosufficient temperatures or to actinic radiation for a limited period oftime and/or by increasing the intensity of the activation energy, i.e.increasing the temperature and/or the intensity of the light.

Furthermore, it is to be appreciated that the initiators may be presentin different phases in different amounts. For example, an initiator foreffecting polymerization of the monomers/oligomers of the first oilphase may be present in either the first or second oil phase compositionor both, but is preferably in the first so that the initiator may beactivated prior to combining with the second oil phase, which containsthe wall forming (meth)acrylate monomers, so as to enhance and/or speedup the polymerization/oligomerization. Additionally, as noted above, aninitiator for the wall forming materials of one phase may be in theother phase whereby said initiator helps ensure polymerization at theoil/water interface. This is especially effective where the initiatorhas a greater affinity for the other phase and tends to concentrate atthe interface. Of course such additional initiator is not necessary,especially where there is sufficient initiator in the phase of the wallforming material that it initiates.

Dual Water Phase Microencapsulation

As noted, the dual acrylic/melamine walled microcapsules of the presentteaching may also be formed in a wholly aqueous based microcapsule wallforming system employing at least two aqueous phase compositions: one ofwhich comprises a curable, water soluble or water dispersible(meth)acrylate ester composition and the other the water soluble orwater dispersible melamine resin composition. As with the oil/waterphase dual walled system, it is also possible to form an acryliccore/melamine outer shell microcapsule as well as a melaminecore/acrylic outer shell microcapsule. For the sake of convenience andsimplicity, the following discussion will focus on the latter; thoughthose skilled in the art will readily recognize and be able to apply theteachings presented herein to form the former.

The dual water phase dual walled microcapsules are typically formed by asequential microencapsulation process wherein a first shell wall isformed of one of the two wall forming compositions on the disperseddroplets of the core material before that single walled microcapsule iscombined with the second water phase wall forming material to form anover-shell or over-layer of the second wall forming material on thepreviously formed microcapsule: in essence the second wall formingmaterial will encapsulate the microcapsule formed from the first wallforming material. Alternatively, the second water phase wall formingmaterial may be added, in whole or in part, preferably in part, beforeor concurrent with/during the polymerization of the first wall formingmaterial and polymerized concurrent with the polymerization of the firstwall forming material. Here, it is most typical that polymerization ofthe first water phase wall forming material is initiated prior toinitiation of the second water phase wall forming material: though bothpolymerizations will proceed concurrently until completed.

Generally speaking, in the dual water phase microencapsulation processthe water phase (meth)acrylate monomers/oligomers comprise from 5-90,preferably from 10-70, more preferably from 20-50, most preferably from30-40 weight percent and the melamine resin wall forming materialscomprise from 10-95, preferably from 30-90, more preferably from 50-80,most preferably from 60-70 weight percent, based on the total weight ofthe wall forming materials.

Typically the first step of this process is the preparation of anaqueous medium or matrix in a reactor vessel which will serve as themedium in which the microencapsulation process will take place.Initially the aqueous medium comprising water and select emulsifiers forthe microencapsulation process at hand is prepared under moderate mixingat room temperature. Optionally, the aqueous medium may also contain aportion or all of the wall forming materials, including monomer,oligomer and/or prepolymer and initiator. As appropriate, it may benecessary to adjust the pH of the medium to optimize themicroencapsulation process. Preferably, the pH is adjusted to 5.8 orthereabouts, typically through the addition of a sodium hydroxidesolution.

The second step is the formation of the emulsion of the core materialthat is to be encapsulated. Here the core material, which comprises orcontains the ingredient or other material that is to be encapsulated, isadded to the aqueous medium and subjected to high shear mixing ormilling, typically ˜1200 rpm milling. In many instances the corematerial itself is an oil, e.g., a scented oil. Additionally, it is alsocontemplated that one or more of the monomers and/or oligomers of theinitial wall forming materials or a portion thereof is added to theaqueous medium just prior to, concurrent with or subsequent to theaddition of the core material. The contents of the reactor vessel aresubjected to the milling process until the desired particle size isattained, typically 20-30 minutes. Generally, at this point a sample ofthe emulsion in the making is taken periodically and the particle sizedetermined so as to avoid over-emulsification.

Once the desired emulsion is established and stable, the degree of themixing is reduced, typically the milling blade is replaced with aconventional mixer blade or other mixer element, and a slower mixingensued. Thereafter the remaining constituents or ingredients necessaryfor the formation of the initial shell wall is added to and intimatelymixed with the contents of the reactor vessel: these include the wallforming materials or, as appropriate, the balance of the same and mayalso include additional emulsifiers, etc.

The contents of the reactor vessel are then subjected to conditionswhich effect polymerization of the wall forming material and thepolymerization allowed to continue for several hours until completed ornearly so.

The microcapsules formed in the previous step are then subjected to asecond encapsulation process employing another water phase compositioncomprising the ingredients or constituents of the second wall formingmaterial to be used. Other ingredients, including additionalemulsifiers, chain transfer agents, etc. may also be added at thispoint. In any event, once the second water phase wall formingcomposition is combined with the reaction mix containing the preformedmicrocapsules, the mixture is subjected to such conditions as willeffect deposition and polymerization of the second wall formingcomposition on the outer wall of the previously formed microcapsule.This processing is continued until the polymerization is completedand/or the desired wall thickness or microcapsule size is attained.

In yet another embodiment, one may add the second water phasecomposition comprising the ingredients or constituents of the secondwall forming material to the aforementioned emulsion concurrent with orimmediately or subsequently following the initiation of thepolymerization of the first wall forming materials rather than waitingfor several hours or until after completion of the polymerization of thefirst wall forming materials. In this instance, wall formation occurssimultaneously with the development of an interpenetrating networkand/or copolymerization at the interface of the two materials.

As with the dual water/oil microencapsulation process describedpreviously, the all water phase microencapsulation process generalizedin the preceding paragraphs may be altered in a variety of ways,changing and/or adding additional ingredients, altering the sequence ofsteps, etc. Attention is directed to the preceding discussion inrelation to the oil/water phase microcapsules as those variations areequally applicable to the water phase only microencapsulation process aswell and is not repeated in the interest of expediency.

Having spoken in generalities, the following describes more specificallythe preparation of a water phase acrylic/melamine dual walledmicrocapsule which is produced as follows:

(I) a first water phase composition comprising water, one or moreemulsifiers for emulsifying an oil in water is prepared in a reactorvessel at room temperature at a low mixer speed (350 rpm). As necessary,the pH of the first water phase composition is adjusted to a pH of ˜5(5-6) with a suitable material such as sodium hydroxide.

(II) once the first water phase material is formed and essentiallystable or homogenous, a portion, ˜38% by weight (30-40%), of themelamine wall forming material is slowly added to the reactor vesselwith continued mixing. This material is allowed to mix for approximately20 minutes (15-25 minutes) with constant stirring and the temperatureelevated to 53° C. (50° C.-60° C.) and held.

(III) an oil phase core material, i.e., the material to be encapsulated,typically an aromatic oil, is slowly added to the reactor vessel undermilling conditions, i.e., high shear mixing, ˜1200 rpm until the desireddroplet size is attained, approximately 20 (20-60) minutes or so. Duringthis phase, samples are periodically taken from the milling vessel tocheck droplet size. Once the desired droplet size is attained, themixing is stopped and the milling blade replaced with a mixing blade.

(VI) a second water phase composition comprising water, the remainder ofthe water phase melamine resin wall forming materials and an initiatorfor initiating, accelerating and/or catalyzing the condensation of themelamine resin, which had been previously mixed and heated to 50° C.(50° C.-60° C.) and whose pH has been adjusted to 5.8 (pH 5-6), is thenslowly added to the reaction vessel over a period of several minutes andthe mixture allowed to mix for several more minutes.

(VIII) a salt, e.g., disodium sulfate, is added to the mixture over aperiod of a minute or two and the mixture then subjected to higher speedmixing, ˜600 rpm.

(IX) the temperature of the reactor vessel in increased to 85° C. andthe contents of the reactor vessel allowed to “cook” for a period of 8hours with continued mixing.

(X) towards the end of the “cooking”, a third water phase composition isprepared comprising water and a free radical initiator in a mixingvessel and the contents mixed. As necessary, the pH of the mixture isadjusted to 4.6 (pH 4.5-6) with, e.g., sodium hydroxide, and the mixtureheated to a temperature of 60° C. (50-75° C.) and the temperature heldfor a period of 30 minutes (25-45). Generally, pH is adjusted to aid insolubility of the initiator and/or other component.

(XI) concurrently, a fourth water phase composition is preparedcomprising water and the free radical polymerizable (meth)acrylate wallforming monomers/-oligomers.

(XII) the third and fourth water phase compositions are then mixedtogether at room temperature (20-30° C.) and mixed for a period of 10minutes after which time they are added to the reaction mixture and thetemperature of the mixture is further elevated to 95° C. over a periodof 60 minutes and held at that temperature for an additional 6 hours toform the final microcapsules.

The microcapsules formed in accordance with the present teachings may berecovered by conventional methods and employed in conventionalapplications as well as applications demanding of the specificproperties and characteristics of the microcapsules so formed. Thesemicrocapsules are especially suitable for use in applications where themicrocapsules are subject to erosion or wear and thus require goodphysical properties to resist premature fracture combined with adequateleakage or release of the contents, especially perfumes, to provide adetectable, to the nose, level of release, without too much release, thelatter resulting in poor life to the treatment of the treated products.These microcapsules are especially suited for use in fabric treatments.

Having described the general dual walled microcapsules and their methodof manufacture, attention is now given to the critical as well astypical and optional ingredients that may be used and are suitable foruse in the practice of the present teachings.

Acrylic Wall Forming Compositions

As noted above, there are two different types of acrylic wall formingcompositions that may be used in the practice of the present teachingsdepending upon the desired microcapsules and methodology for theirproduction: one comprising oil soluble or dispersible (meth)acrylatemonomers, oligomers and/or prepolymers and the other water soluble ordispersible (meth)acrylate monomers, oligomer and/or prepolymers. Inboth instances, the (meth)acrylate may be pre-polymerized to formoligomers/prepolymers of the precursors of each.

Oil Soluble or Dispersible (Meth)Acrylates

The (meth)acrylate wall forming components of the oil phase, in the caseof a two phase, oil/water, system, comprise either (A)(i) at least oneoil soluble or dispersible amine (meth)acrylate, (ii) at least one oilsoluble or dispersible acidic (meth)acrylate or at least one oil solubleor dispersible simple acid or both, and (iii) at least one oil solubleor dispersible multifunctional (meth)acrylate monomer or oligomer or (B)(i) at least one oil soluble or dispersible acidic (meth)acrylate, (ii)at least one oil soluble or dispersible simple base, and (iii) at leastone oil soluble or dispersible multifunctional (meth)acrylate monomer oroligomer. Although the processes of the present teaching may employ asingle composition containing all three of the aforementioned requiredcomponents or two or more precursor compositions each containing one ormore of the aforementioned required components, it is preferred that theprocess employ a preformed oligomer or prepolymer of said components orthat said oligomer or prepolymer be formed in-situ in the course,preferably immediately prior to, the initiation of the actual formationof the shell wall at the interface of the oil and water phases. Wherethe (meth)acrylate oligomer/prepolymer is formed in-situ as part of theoverall microencapsulation process, the oil phase composition willtypically comprise at least a first oil phase composition and a secondoil phase composition, one of which comprises the combination of (A)(i)at least one oil soluble or dispersible amine (meth)acrylate, (ii) atleast one oil soluble or dispersible acidic (meth)acrylate or at leastone oil soluble or dispersible simple acid or both, and (iii) at leastone oil soluble or dispersible multifunctional (meth)acrylate monomer oroligomer or (B) (i) at least one oil soluble or dispersible acidic(meth)acrylate, (ii) at least one oil soluble or dispersible simplebase, and (iii) at least one oil soluble or dispersible multifunctional(meth)acrylate monomer or oligomer and the other an initiator forforming the (meth)acrylate oligomer/prepolymer and, optionally, aninitiator, which may be the same or a similar initiator, for effectingpolymerization of the so formed (meth)acrylate oligomer/prepolymer toform the microcapsule wall.

Suitable oil-soluble or dispersible amine (meth)acrylates for use in thepractice of the present method include, by way of illustration and notlimitation, amine modified (meth)acrylate monomers such as mono ordiacrylate amines, mono or dimethacrylate amines, amine modifiedpolyetheracrylates, amine modified polyethermethacrylates, aminoalkylacrylates, aminoalkyl methacrylates and the like. The amines can includeprimary, secondary or tertiary amines.

Preferably, the amine (meth)acrylate is an aminoalkyl acrylate oraminoalkyl methacrylate including, for example, but not by way oflimitation, ethylaminoethyl acrylate, ethylaminoethyl methacrylate,aminoethyl acrylate, aminoethyl methacrylate, tertiarybutyl ethylaminoacrylate, tertiarybutyl ethylamino methacrylate, tertiarybutylaminoethyl acrylate, tertiarybutyl aminoethyl methacrylate diethylaminoacrylate, diethylamino methacrylate, diethylaminoethyl acrylate,diethylaminoethyl methacrylate, dimethylaminoethyl acrylate anddimethylaminoethyl methacrylate. More preferably, the amine(meth)acrylate is an aminoethylacrylate or aminoethylmethacrylate, mostespecially tertiarybutyl aminoethyl methacrylate, because these arereadily available and give good results

Most preferably, the oil-soluble or dispersible amine acrylate or aminemethacrylate corresponds to the formula:

wherein R₁ is hydrogen or methyl and each R₂ and R₃ is independentlyselected from hydrogen and C₁-C₁₂ hydrocarbon.

In those instances where an oil soluble or dispersible simple base is tobe employed in place of or in addition to the amine (meth)acrylate, thesimple base is typically a primary, secondary or tertiary amine or aminocompound including, for example, aliphatic amines, cycloaliphaticamines, amidoamines and polyamides. Specific exemplary amines includediethylene triamine, triethylenetetraamine and tetraethylenepentaamine,Lewis bases such as o-(diethylaminoethyl)phenol,tris-(dimethylaminomethyl)phenol and 2-ethyl-4-methyl imidazole base;and Schiff bases such as methyl anthranilate/citronellal Schiff base,isononylaldehyde/methylanthranilate Schiff base, methylN-(3,7-dimethyl-7-hydroxyoctylidene)-anthranilate Schiff-base.

Suitable oil-soluble or dispersible (meth)acrylate acids generallycorrespond to the formula:

wherein R₁ is hydrogen or methyl and R₄ is a straight chain or branchedC₁-C₁₀ hydrocarbyl group and the carboxyl moiety, —COOH, is bonded toany of the carbon atoms of the hydrocarbyl group; preferably, theterminal carbon atom. Exemplary acid (meth)acrylates include2-carboxyethyl acrylate and 2-carboxyethyl methacrylate.

In those instances where an oil soluble or dispersible simple acid is tobe employed in place of or in addition to the acid (meth)acrylate, theoil soluble acid is preferably an organic acid. The organic acid can beselected from various acids such as carboxy acids, with monoalkylmaleates such as monomethyl-, monoethyl- or monobutyl-maleate beingpreferred, with monobutyl maleate being most preferred. Other preferredorganic acids include beta-carboxyethyl acrylate. Yet other organicacids that can be usefully employed in the invention include, organicsulfonic acids such as alkyl benzene sulfonic acid, more particularlylinear alkyl benzene sulfonic acid, tridecylbenzene sulfonic acid, moreparticularly linear trialkylbenzene sulfonic acid such as lineartridecylbenzene sulfonic acid, alkyldiphenyloxide sulfonic acid,preferably dodecyl diphenyloxide disulfonic acid, more particularlybranched C₁₂ diphenyloxide disulfonic acid, alkylbenzene sulfonic acid,more particularly, dodecyl benzene sulfonic acid, dialkylnaphthalenedisulfonic acid, more particularly dinonylnaphthalene disulfonic acid,4-hydrozino benzene sulfonic acid, acrylic acid, methacrylic acid, andthe like. Desirably the organic acid is selected to be dispersible inthe oil phase and sparingly soluble in the water phase.

Finally, the oil-soluble or dispersible multifunctional (meth)acrylatemonomers and oligomers contain two or more double bonds, preferably twoor more acrylate or methacrylate functional groups. Suitable monomersand oligomers include, by way of illustration and not limitation, allylmethacrylate; triethylene glycol dimethacrylate; ethylene glycoldimethacrylate; diethylene glycol dimethacrylate; aliphatic or aromaticurethane acrylates, such as hexa-functional aromatic urethane acrylates;ethoxylated aliphatic difunctional urethane methacrylates; aliphatic oraromatic urethane methacrylates, such as tetra-functional aromaticmethacrylates; epoxy acrylates; epoxymethacrylates; tetraethylene glycoldimethacrylate; polyethylene glycol dimethacrylate; 1,3 butanedioldiacrylate; 1,4-butanediol dimethacrylate; 1,4-butanediol diacrylate;diethylene glycol diacrylate; 1,6 hexanediol diacrylate; 1,6 hexanedioldimethacrylate; neopentyl glycol diacrylate; polyethylene glycoldiacrylate; tetraethylene glycol diacrylate; triethylene glycoldiacrylate; 1,3 butylene glycol dimethacrylate; tripropylene glycoldiacrylate; ethoxylated bisphenol A diacrylate; ethoxylated bisphenol Adimethylacrylate; dipropylene glycol diacrylate; alkoxylated hexanedioldiacrylate; alkoxylated cyclohexane dimethanol diacrylate; propoxylatedneopentyl glycol diacrylate; trimethylolpropane tri methacrylate;trimethylolpropane triacrylate; pentaerythritol triacrylate;pentaerythritol tetramethacrylate; ethoxylated trimethylolpropanetriacrylate; propoxylated trimethylolpropane triacrylate; propoxylatedglyceryl triacrylate; ditrimethylolpropane tetraacrylate; dipentaerythritol pentaacrylate; ethoxylated pentaerythritoltetraacrylate; bis-phenol A diacrylate; bis-phenol A dimethacrylate,hexa-functional aromatic urethane acrylate; hexa-functional aromaticurethane methacrylate; and the like.

Generally speaking, the make-up of the oligomer/prepolymer of first oilphase composition or, if formed in-situ in the process of the presentinvention, the combination of reactants in the first oil phase is asfollows:

-   -   0.1 to 15%, preferably 0.2 to 10%, more preferably 0.4 to 5% by        weight of the amine (meth)acrylate and/or simple base;    -   0.1 to 15%, preferably 0.2 to 10%, more preferably 0.4 to 5% by        weight of the acid (meth)acrylate and/or simple acid; and    -   99.8 to 70%, preferably 99.6 to 80%, more preferably 99.2 to 90%        of the multifunctional (meth)acrylate:

provided that when the simple base or the simple acid is present it isalso employed in a mole ratio of from 5:1 to 1:5, preferably 3:1 to 1:3,of the acid to amine (meth)acrylate or of the base to acid(meth)acrylate.

When the (meth)acrylate oligomer/prepolymer is formed in-situ as a partof the overall microencapsulation process, the oil phase composition,will comprise a mixture of the specified monomers and, if present,oligomers which are then subjected to such conditions as will effectpolymerization thereof. If necessary, though preferably, an initiator isadded to the mixture, typically as part of another oil phase compositionor component, which initiator is then activated to initiatepolymerization of the monomers and, if present, oligomers. For example,in the case of a free radical initiator, the mixture is subjected tosuch conditions as will generate sufficient free radicals to effect thedesired oligomerization/pre-polymerization. Once initiated,polymerization is allowed to proceed for only a set period of time toform the (meth)acrylate oligomer/prepolymer, but not long enough to (a)complete polymerization or (b) form high molecular weight polymers whichare incapable of moving within oil phase in which they are solubilizedor dispersed and/or fail to stay in solution. Generally speaking, themolecular weight of the preformed or in-situ formed meth(acrylate)oligomer/prepolymer is less than 1,000,000, preferably less than500,000. Most preferably, these oligomers/prepolymers have a molecularweight of from 5,000 to 200,000, more preferably 10,000 to 100,000.Polymerization may be stopped by removing the conditions that induce oractivate the initiator. If present, the amount of the initiator will befrom 0.1 to 10%, preferably 0.1 to 6%, more preferably 0.5 to 2.5% byweight based on the weight of the oil phase.

Water Soluble or Dispersible (Meth)Acrylates

Alternatively, as noted, the shell wall may comprise an acrylic polymerderived from water soluble or dispersible (meth)acrylate monomer,oligomers and/or prepolymers. Those skilled in the art will readilyrecognize and appreciate that many of the acrylate monomers andoligomers disclosed above for use in the oil phase will have some watersolubility or water dispersability, particularly in the presence of asuitable emulsifier and/or other solubilizer or by suitable elevatedtemperature and/or pH adjustment, and may be used in forming suitableaqueous based (meth)acrylic ester wall forming compositions. Similarly,they will recognize and appreciate other (meth)acrylic esters thatpossess water solubility, even low water solubility, and/or waterdispersibility so as to be suitable for use in the practice of thepresent teachings.

Generally speaking, suitable water soluble and/or dispersible(meth)acrylate monomers and low molecular weight oligomers contain at aleast one acrylate or methacrylate group and comprise a hydrocarbonportion that is small relative to the whole of the monomer or oligomersuch that the ester functional group is enough to impart sufficienthydrophilicity to the monomer, as is the case with, for example,1,3-butanediol diacrylate. In the case of higher molecular weightmonomers, oligomers and/or prepolymers these monomers, oligomers and/orprepolymers will have a sufficient number of acrylate and/ormethacrylate groups and/or, again, comprise a relatively smallhydrocarbon portion relative to the whole of the monomer, oligomerand/or prepolymer to impart sufficient hydrophilicity thereto.Otherwise, the hydrophobicity of the larger hydrocarbon portion oflarger acrylate ester monomers, oligomers and/or prepolymers may beovercome by the presence of additional functional groups such as amines,urethanes, alcohols or ethers or combinations thereof which enhance thehydrophilicity. Exemplary water soluble or dispersible acrylates ormethacrylates include amine modified polyether (meth)acrylate oligomers,hexafunctional aromatic urethane (meth)acrylate oligomers, hydroxyethyl(meth)acrylate, hydroxypropyl (meth)acrylate, methyl methacrylate,butanediol di(meth)acrylate, hexanediol di(meth)acrylate, ethoxylatedbisphenol-A diacrylate, ethoxylated bisphenol-A dimethacrylate,isobornyl (meth)acrylate, pentaerythritol tri(meth)acrylate,pentaerythritol tetra(meth)acrylate, penta(meth)acrylate ester,diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate,triethylene glycol di(meth)acrylate, tripropylene glycoldi(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropanetri(meth)acrylate, methoxy polyethylene glycol mono(meth)acrylate,ethoxylated trimethylolpropane tri(meth)acrylate, and ethoxylatedpentaerythritol tetra(meth)acrylate, difunctional aliphatic epoxy(meth)acrylates, polyethylene glycol di(meth)acrylate, polypropyleneglycol di(meth)acrylate, alkoxylated mono- or multi-functional(meth)acrylate ester, polyester (meth)acrylate oligomers, amine modifiedpolyether (meth)acrylate oligomers and the like. Especially preferredwater soluble or water dispersible (meth)acrylates are the polyethyleneglycol di(meth)acrylates, ethoxylated mono- or multi-functional(meth)acrylates, and (meth)acrylate monomers and/or oligomers that arecapable of being dispersed in water with a small amount of a suitableemulsifier and/or solubilizer.

Though the foregoing discussion mostly describes various acrylicmonomers and oligomers, acrylic prepolymers and low molecular weightpolymers, including co-polymers, are also suitable. For example, theacrylic component may be a polyacrylic acid or a copolymer of acrylicacid and an alkyl acrylate. The alkyl acrylate can be selected such thatthe alkyl moiety is from about one to twelve and preferably from one toeight carbons. Examples of such alkyl acrylates include methyl acrylate,ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate,hexylacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate and the like.A preferable copolymer was 90% polyacrylic acid and 10% butyl acrylate.Exemplary acrylic polymers include Colloid 121 and Colloid 351 fromRhone Poulenc.

Although 100% of the water phase (meth)acrylate may be one or moremulti-functional (meth)acrylate monomers/oligomer or one or more mono-and/or di-functional (meth)acrylate monomers/oligomers, generallyspeaking the water phase (meth)acrylate wall forming compositioncomprises from 10-95, preferably 20-85, more preferably, 35-70, mostpreferably 50-65 weight percent of the one or more multi-functional(meth)acrylate monomers and/or oligomers and from 5-90, preferably15-85, more preferably 30-65, most preferably 35-50 weight percent of athe one or more mono- and/or di-functional, preferably or predominatelydi-functional, (meth)acrylate monomer and/or oligomer, based on thetotal weight of the water phase (meth)acrylate wall forming material.These water phase (meth)acrylate wall forming materials, both in termsof chemical make-up and formulation (i.e., relative weight percent) arealso disclosed in U.S. Provisional Patent Application No. 62/064,906filed on Oct. 16, 2014, the contents of which are hereby incorporated byreference.

Melamine Resin

The second critical wall forming material is the melamine resinprepolymer or the precursors therefore. Microcapsule wall formingmelamine prepolymers and precursors therefore are well known and widelyavailable. These include, for example, melamine-based polyureas,melamine-formaldehyde resins, melamine-aldehyde resins, dimethylolmelamine urea, methylated dimethylol melamine urea, methylated melamineformaldehyde, methylated methylol melamine, and mixtures of melamineformaldehyde with urea formaldehyde. Encapsulations based onpolymerization of melamine-urea and formaldehyde, monomeric or lowmolecular weight polymers of dimethylol urea or methylated dimethylolurea, melamine and formaldehyde, methylated melamine formaldehyde,monomeric or low molecular weight polymers of methylol melamine ormethylated methylol melamine, as taught in U.S. Pat. No. 4,552,811(which is hereby incorporated herein by reference) are preferable.

Though a wide variety of melamine prepolymers and precursors aresuitable for use in the practice of the present teachings, especiallypreferred melamine prepolymers and precursors are those that areformaldehyde free and/or those of the methylated melamine resins thatare wholly or partially soluble in water, most especially the partiallymethylated and high imino methylated melamine resins. These preferredmelamine prepolymers are reactive with hydroxyl, carboxyl and amidfunctional groups of other monomers, oligomers, prepolymers and/orpolymers. Most importantly, it is especially desirable in the preferredembodiments that the melamine prepolymers are capable ofself-condensation to form their own polymers and more preferably have amoderate to high tendency to self-condensate. Though not required,polymerization of these melamine prepolymers is aided by acid catalysis.Of these preferred melamine prepolymers, their functionality ispredominately methoxymethyl and methylol in the case of the partiallymethylated melamines and methoxymethyl and imino in the case of themethylated high imino melamines. These melamine resins are also wellknown and widely available. Exemplary resins include those availablefrom Allnex USA, Stamford, Conn. including those sold under thetradename Cymel such as Cymel 328, Cymel 385 and Cymel 373.

Core Ingredient

The microcapsules of the present teaching include a core material whichcomprises one or more ingredients that are intended to be encapsulated.The core material are selected from a number of different materials suchas chromogens and dyes, flavorants, perfumes, sweeteners, fragrances,oils, fats, pigments, cleaning oils, pharmaceuticals, pharmaceuticaloils, perfume oils, mold inhibitors, antimicrobial agents, adhesives,phase change materials, scents, fertilizers, nutrients, and herbicides:by way of illustration and without limitation. The core material can bea liquid or a solid. With cores that are solid at ambient temperatures,the wall material can usefully enwrap less than the entire core forcertain applications where availability of, for example, an agglomeratecore is desired on application. Such uses can include scent release,cleaning compositions, emollients, cosmetic delivery and the like. Wherethe microcapsule core is phase change material, uses can include suchencapsulated materials in mattresses, pillows, bedding, textiles,sporting equipment, medical devices, building products, constructionproducts, HVAC, renewable energy, clothing, athletic surfaces,electronics, automotive, aviation, shoes, beauty care, laundry, andsolar energy.

The core material can be a minor or major constituent of the materialencapsulated by the microcapsules. Typically, particularly when the corematerial is a liquid material, the core material is combined with one ormore of the compositions from which the internal wall of themicrocapsule is formed. For example, if the microcapsule has a(meth)acrylic inner wall formed of two oil phase compositions, the corematerial will be combined with one or the other of such compositions ora portion of the core material may be present in each. If the corematerial can function as the oil solvent in the capsules, e.g. acts asthe solvent or carrier for the wall forming materials, it is possible tomake the core material the major or total material encapsulated. Usuallyhowever, the core material is from 0.01 to 99 weight percent of thecapsule internal contents, preferably 0.01 to about 65 by weight of thecapsule internal contents, and more preferably from 0.1 to about 45% byweight of the capsule internal contents. With certain applications, thecore material can be effective even at just trace quantities.

Oil Phase Carriers and Solvents

Where the core material is not itself sufficient to serve as the oilphase or solvent, particularly for the wall forming materials, the oilphase will further include a suitable carrier and/or solvent. Thesecarriers or solvents preferably have a boiling point greater than 100°C. and low volatility and are non-flammable. Though not limited thereto,they preferably comprise one or more esters, preferably with chainlengths of up to 18 carbon atoms or even up to 42 carbon atoms and/ortriglycerides such as the esters of C₆ to C₁₂ fatty acids and glycerol.Exemplary carriers and solvents include, but are not limited to:ethyldiphenylmethane; butyl biphenyl ethane; benzylxylene; alkylbiphenyls such as propylbiphenyl and butylbiphenyl; dialkyl phthalatese.g. dibutyl phthalate, dioctylphthalate, dinonyl phthalate andditridecylphthalate; 2,2,4-trimethyl-1,3-pentanediol diisobutyrate;alkyl benzenes such as dodecyl benzene; alkyl or aralkyl benzoates suchas benzyl benzoate; diaryl ethers; di(aralkyl)ethers and aryl aralkylethers; ethers such as diphenyl ether, dibenzyl ether and phenyl benzylether; liquid higher alkyl ketones (having at least 9 carbon atoms);alkyl or aralkyl benzoates, e.g., benzyl benzoate; alkylatednaphthalenes such as dipropylnaphthalene; partially hydrogenatedterphenyls; high-boiling straight or branched chain hydrocarbons;alkaryl hydrocarbons such as toluene; vegetable and other crop oils suchas canola oil, soybean oil, corn oil, sunflower oil, cottonseed oil,lemon oil, olive oil and pine oil; methyl esters of fatty acids derivedfrom transesterification of vegetable and other crop oils, includingthose mentioned previously; methyl ester of oleic acid; esters ofvegetable and other crop oils, e.g. soybean methyl ester; straight chainsaturated paraffinic aliphatic hydrocarbons of from 10 to 13 carbons,and the like. Mixtures of the above can also be employed. Commondiluents such as straight chain hydrocarbons can also be blended withthe solvents, or blend of solvents. In those cases where the inner wallof the microcapsule is oil-based derived, the solvent is typicallyselected on the basis of their hydrophobicity and their ability todisperse or solvate the wall forming monomers and/or prepolymer of theoil phase.

Emulsifier

Optionally, though preferably, where microencapsulation process involvesa water phase-oil phase system, the water phase composition or, in thecase of microcapsules prepared from two or more water phasecompositions, one or both of said water phase compositions will containan emulsifier to aid in the creation of the dispersion of the oil phasein the continuous water phase or, as appropriate, the water phase in thecontinuous oil phase. Similarly, where dual water phase wall formingmaterials are employed an emulsifier is employed to disperse the corematerial, which is typically an oil or oil phase material, in that waterphase. Less critical, but again, preferably, an emulsifier, preferably anon-ionic emulsifier, is added to one or both water phase compositionsto aid in the dispersion and/or solubility of the water soluble ordispersible acrylate monomer or oligomer and/or the melamine resin, asappropriate.

Emulsifiers of all types are suitable for use in the practice of thepresent invention though it is to be appreciated, and those skilled inthe art will readily recognize, that different systems, e.g., differentfirst oil phase compositions and/or core material, will be better suitedwith one or more classes of emulsifiers than others. Specifically, whilethe present teachings are applicable to anionic, cationic, non-ionic andamphoteric emulsifiers generally, preferred emulsifiers are the cationicand non-ionic emulsifiers, particularly those having polyalkyletherunits, especially polyethylene oxide units, with degrees ofpolymerization of the alkylene ether unit of greater than about 6.Preferred emulsifiers are those which significantly reduce theinterfacial tension between the aqueous phase and dispersed phase, andthereby reduce the tendency for droplet coalescence. In this regard,generally the emulsifiers for use in the first water phase for aiding inthe oil in water emulsion or dispersion will have HLB values of from 11to 17. While emulsifiers of the same HLB value may also be used in thesecond water phase, those emulsifiers that are used to enhance thesolubility and/or dispersibility of the water phase (meth)acrylate inthe second water phase will generally have HLB values of 16 to 20. Ofcourse, emulsifiers/surfactants of lower and higher HLB values thatachieve the same objective as noted are also included.

Exemplary anionic surfactants and classes of anionic surfactantssuitable for use in the practice of the present invention include:sulfonates; sulfates; sulfosuccinates; sarcosinates; alcohol sulfates;alcohol ether sulfates; alkylaryl ether sulfates; alkylaryl sulfonatessuch as alkylbenzene sulfonates and alkylnaphthalene sulfonates andsalts thereof; alkyl sulfonates; mono- or di-phosphate esters ofpolyalkoxylated alkyl alcohols or alkylphenols; mono- ordi-sulfosuccinate esters of C₁₂ to C₁₅ alkanols or polyalkoxylated C₁₂to C₁₅ alkanols; ether carboxylates, especially alcohol ethercarboxylates; phenolic ether carboxylates; polybasic acid esters ofethoxylated polyoxyalkylene glycols consisting of oxybutylene or theresidue of tetrahydrofuran; sulfoalkylamides and salts thereof such asN-methyl-N-oleoyltaurate Na salt; polyoxyalkylene alkylphenolcarboxylates; polyoxyalkylene alcohol carboxylates alkylpolyglycoside/alkenyl succinic anhydride condensation products; alkylester sulfates; naphthalene sulfonates; naphthalene formaldehydecondensates; alkyl sulfonamides; sulfonated aliphatic polyesters;sulfate esters of styrylphenyl alkoxylates; and sulfonate esters ofstyrylphenyl alkoxylates and their corresponding sodium, potassium,calcium, magnesium, zinc, ammonium, alkylammonium, diethanolammonium, ortriethanolammonium salts; salts of ligninsulfonic acid such as thesodium, potassium, magnesium, calcium or- ammonium salt; polyarylphenolpolyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates;and sulfated alkyl phenol ethoxylates and phosphated alkyl phenolethoxylates; sodium lauryl sulfate; sodium laureth sulfate; ammoniumlauryl sulfate; ammonium laureth sulfate; sodium methyl cocoyl taurate;sodium lauroyl sarcosinate; sodium cocoyl sarcosinate; potassium cocohydrolyzed collagen; TEA (triethanolamine) lauryl sulfate; TEA(Triethanolamine) laureth sulfate; lauryl or cocoyl sarcosine; disodiumoleamide sulfosuccinate; disodium laureth sulfosuccinate; disodiumdioctyl sulfosuccinate; N-methyl-N-oleoyltaurate Na salt;tristyrylphenol sulphate; ethoxylated lignin sulfonate; ethoxylatednonylphenol phosphate ester; calcium alkylbenzene sulfonate; ethoxylatedtridecylalcohol phosphate ester; dialkyl sulfosuccinates; perfluoro(C₈-C₁₈)alkyl phosphonic acids; perfluoro(C₆-C₁₈)alkyl-phosphinic acids;perfluoro(C₃-C₂₀)alkyl esters of carboxylic acids; alkenyl succinic aciddiglucamides; alkenyl succinic acid alkoxylates; sodium dialkylsulfosuccinates; and alkenyl succinic acid alkylpolyglycosides. Furtherexemplification of suitable anionic emulsifiers include, but are notlimited to, water-soluble salts of alkyl sulfates, alkyl ether sulfates,alkyl isothionates, alkyl carboxylates, alkyl sulfosuccinates, alkylsuccinamates, alkyl sulfate salts such as sodium dodecyl sulfate, alkylsarcosinates, alkyl derivatives of protein hydrolyzates, acylaspartates, alkyl or alkyl ether or alkylaryl ether phosphate esters,sodium dodecyl sulphate, phospholipids or lecithin, or soaps, sodium,potassium or ammonium stearate, oleate or palmitate, alkylarylsulfonicacid salts such as sodium dodecylbenzenesulfonate, sodiumdialkylsulfosuccinates, dioctyl sulfosuccinate, sodiumdilaurylsulfosuccinate, poly(styrene sulfonate) sodium salt,alkylene-maleic anhydride copolymers such as isobutylene-maleicanhydride copolymer, or ethylene maleic anhydride copolymer gum arabic,sodium alginate, carboxymethylcellulose, cellulose sulfate and pectin,poly(styrene sulfonate), pectic acid, tragacanth gum, almond gum andagar; semi-synthetic polymers such as carboxymethyl cellulose, sulfatedcellulose, sulfated methylcellulose, carboxymethyl starch, phosphatedstarch, lignin sulfonic acid; maleic anhydride copolymers (includinghydrolyzates thereof), polyacrylic acid, polymethacrylic acid, acrylicacid alkyl acrylate copolymers such as acrylic acid butyl acrylatecopolymer or crotonic acid homopolymers and copolymers,vinylbenzenesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acidhomopolymers and copolymers, and partial amide or partial ester of suchpolymers and copolymers, carboxy modified polyvinyl alcohol, sulfonicacid-modified polyvinyl alcohol and phosphoric acid-modified polyvinylalcohol, phosphated or sulfated tristyrylphenol ethoxylates.

Exemplary amphoteric and cationic emulsifiers includealkylpolyglycosides; betaines; sulfobetaines; glycinates; alkanol amidesof C₈ to C₁₈ fatty acids and C₈ to C₁₈ fatty amine polyalkoxylates; C₁₀to C₁₈ alkyldimethylbenzylammonium chlorides; coconutalkyldimethylaminoacetic acids; phosphate esters of C₈ to C₁₈ fattyamine polyalkoxylates; alkylpolyglycosides (APG) obtainable from anacid-catalyzed Fischer reaction of starch or glucose syrups with fattyalcohols, in particular C₈ to C₁₈ alcohols, especially the C₈ to C₁₀ andC₁₂ to C₁₄ alkylpolyglycosides having a degree of polymerization of 1.3to 1.6, in particular 1.4 or 1.5. Additional Cationic emulsifiersinclude quaternary ammonium compounds with a long-chain aliphaticradical, e.g. distearyldiammonium chloride, and fafty amines. Among thecationic emulsifiers which may be mentioned arealkyldimethylbenzylammonium halides, alkyldimethylethyl ammoniumhalides, etc. specific cationic emulsifiers include palmitamidopropyltrimonium chloride, distearyl dimonium chloride, cetyltrimethylammoniumchloride, and polyethyleneimine. Additional amphoteric emulsifiersinclude alkylaminoalkane carboxylic acids betaines, sulphobetaines,imidazoline derivatives, lauroamphoglycinate, sodiumcocoaminopropionate, and the zwitterionic emulsifier cocoamidopropylbetaine.

Suitable non-ionic emulsifiers are characterized as having at least onenon-ionic hydrophilic functional group. Preferred non-ionic hydrophilicfunctional groups are alcohols and amides and combinations thereof.Examples of non-ionic emulsifiers include: mono and diglycerides;polyarylphenol polyethoxy ethers; polyalkylphenol polyethoxy ethers;polyglycol ether derivatives of saturated fatty acids; polyglycol etherderivatives of unsaturated fatty acids; polyglycol ether derivatives ofaliphatic alcohols; polyglycol ether derivatives of cycloaliphaticalcohols; fatty acid esters of polyoxyethylene sorbitan; alkoxylatedvegetable oils; alkoxylated acetylenic diols; polyalkoxylatedalkylphenols; fatty acid alkoxylates; sorbitan alkoxylates; sorbitolesters; C₈ to C₂₂ alkyl or alkenyl polyglycosides; polyalkoxy styrylarylethers; amine oxides especially alkylamine oxides; block copolymerethers; polyalkoxylated fatty glyceride; polyalkylene glycol ethers;linear aliphatic or aromatic polyesters; organo silicones; polyarylphenols; sorbitol ester alkoxylates; and mono- and diesters of ethyleneglycol and mixtures thereof; ethoxylated tristyrylphenol; ethoxylatedfatty alcohol; ethoxylated lauryl alcohol; ethoxylated castor oil; andethoxylated nonylphenol; alkoxylated alcohols, amines or acids; amidesof fatty acids such as stearamide, lauramide diethanolamide, andlauramide monoethanolamide; long chain fatty alcohols such as cetylalcohol and stearyl alcohol; glycerol esters such as glyceryl laurate;polyoxyalkylene glycols and alkyl and aryl ethers of polyoxyalkyleneglycols such as polyoxyethylene glycol nonylphenyl ether andpolypropylene glycol stearyl ether. Polyethylene glycol oligomers andalkyl or aryl ethers or esters of oligomeric polyethylene glycol arepreferred. Also preferred as non-ionic emulsifiers are polyvinylalcohol, polyvinyl acetate, copolymers of polyvinyl alcohol andpolyvinylacetate, carboxylated or partially hydrolyzed polyvinylalcohol, methyl cellulose, various latex materials, stearates,lecithins, and various surfactants. It is known that polyvinyl alcoholis typically prepared by the partial or complete hydrolysis of polyvinylacetate. Accordingly, by reference to polyvinyl alcohol we intend toinclude both completely and partially hydrolyzed polyvinyl acetate. Withrespect to the latter, it is preferred that the polyvinyl acetate be atleast 50 mole % hydrolyzed, more preferably, at least 75 mole %hydrolyzed.

Where the emulsifier is a polymeric emulsifier, especially one having orderived from an acrylic ester, e.g., a polyacrylate, the molecularweight is generally at least 10,000, preferably at least 20,000, mostpreferably 30,000 or more. Additionally, the amount of emulsifier istypically from about 0.1 to about 40% by weight, more preferably fromabout 0.2 to about 15 percent, most preferably from about 0.5 to about10 percent by weight based on the total weight of the formulation. It isto be appreciated that certain acrylic polymers and copolymers mayperform both as an emulsifier as well as a polymerizable and/ornon-polymerizable component in forming the microcapsule wall. Withrespect to the latter, the polymeric emulsifier, particularly those inthe nature of higher molecular weight polymers, are trapped and/orincorporated into the polymer wall as it is formed. This is especiallylikely where the nature of the water phase changes and the solubilizedpolymer comes out of solution.

Chain Transfer Agents

Optionally, though preferably, at least one of the water phasecompositions, particularly the second water phase composition, i.e.,that added to the first, as discussed more clearly below, furtherincludes at least one chain transfer agent. Suitable chain transferagents include, for example, lower alkyl alcohols having from 1 to 5carbon atoms, mercaptoethanol, mercaptopropanol, thioglycolic acid,isooctylmercaptoproprionate, tert-nonylmercaptan, pentaerythritoltetrakis(3-mercapto-proprionate), dodecyl mercaptan, formic acid,halogenated hydrocarbons, such as bromoethane, bromotrichloromethane, orcarbon tetrachloride, and the sulfate, bisulfate, hydrosulfate,phosphate, monohydrogen phosphate, dihydrogen phosphate, toluenesulfonate, and benzoate salts of sodium and potassium, especially sodiumhypophosphite and sodium bisulfate. If present, the chain transferagents are preferably used in amounts ranging from 0.01 to 5%,preferably from 0.5 to 3%, by weight with respect to the monomers and/oroligomers employed.

Initiators

Suitable initiators for effecting polymerization of the various(meth)acrylate monomer, oligomers and/or prepolymers may be added to orpresent in both the oil phase and the water phase compositions.Preferably, an initiator is present in the second oil phase composition,which is free of the aforementioned oil phase (meth)acrylate monomers,oligomers and prepolymers. Similarly, at least one initiator is alsopresent in the first water phase, which is free of the aforementionedwater soluble or water dispersible (meth)acrylate monomers and/oroligomers. In both instances it is desirable to add the initiator to the(meth)acrylate-free compositions so as to avoid unwanted or unintendedpolymerization. By keeping the two separate, one has better control overwhen polymerization is to begin, particularly in processes, like theinstant, where conditions may give rise to activation of the initiatorbefore desired.

Selection of the initiator is dependent, in part, upon the monomers,oligomers and/or prepolymers to be polymerized or further oligomerized,the method by which the initiator is activated, and whether theinitiator is to be present in the oil phase or the water phase.Generally speaking, the preferred initiators are energy activated freeradical initiators meaning that they generate free radicals whensubjected to heat or other energy input. Preferred free radicalinitiators include peroxy initiators, azo initiators, peroxides, andcompounds such as 2,2′-azobismethylbutyronitrile, dibenzoyl peroxide.More particularly, and without limitation the free radical initiator canbe selected from the group of initiators comprising an azo or peroxyinitiator, such as peroxide, dialkyl peroxide, alkyl peroxide,peroxyester, peroxycarbonate, peroxyketone and peroxydicarbonate,2,2′-azobis (isobutylnitrile), 2,2′-azobis(2,4-dimethylpentane-nitrile),2,2′-azobis (2,4-dimethylvaleronitrile),2,2′-azobis(2-methylpropanenitrile), 2,2′-azobis (methylbutyronitrile),1,1′-azobis (cyclohexanecarbonitrile), 1,1′-azobis(cyano-cyclohexane),benzoyl peroxide, decanoyl peroxide; lauroyl peroxide; benzoyl peroxide,di(n-propyl) peroxydicarbonate, di(sec-butyl) peroxydicarbonate,di(2-ethylhexyl) peroxydicarbonate, 1,1-dimethyl-3-hydroxybutylperoxyneodecanoate, .alpha.-cumyl peroxyneoheptanoate, t-amylperoxyneodecanoate, t-butyl peroxyneodecanoate, t-amyl peroxypivalate,t-butyl peroxypivalate, 2,5-dimethyl 2,5-di (2-ethylhexanoyl peroxy)hexane, t-amyl peroxy-2-ethyl-hexanoate, t-butylperoxy-2-ethylhexanoate, t-butyl peroxyacetate, di-t-amyl peroxyacetate,t-butyl peroxide, di-t-amyl peroxide,2,5-dimethyl-2,5-di-(t-butylperoxy)hexyne-3, cumene hydroperoxide,1,1-di-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane,1,1-di-(t-butylperoxy)-cyclohexane, 1,1-di-(t-amylperoxy)-cyclohexane,ethyl-3,3-di-(t-butylperoxy)-butyrate, t-amyl perbenzoate, t-butylperbenzoate, ethyl 3,3-di-(t-amylperoxy)-butyrate, and the like.

Suitable water soluble initiators include the persulfate salts, such asammonium persulfate, sodium persulfate and potassium persulfate;peroxides, such as hydrogen peroxide, oxalic acid peroxide, acetic acidperoxide and succinic acid peroxide; and various water soluble azocompounds such as those represented by the formulas:

In the case of initiators to be used in the water phase, water solubleazo compounds are preferred because they have good decompositiontemperatures.

As noted above, actinic radiation activated initiators are alsocontemplated and desirable. Suitable actinic radiation activatedinitiators include those activated by UV light, IR radiation, visiblelight, electron beam and the like. Actinic radiation activatedinitiators can be used in place of, in whole or in part, heat activatedinitiators. For example, it may be desirable to use heat initiators forone or more polymerization steps and an actinic radiation activatedinitiator for one or more other polymerization steps.

Preferred actinic radiation activated initiators are the UV initiators.Exemplary UV initiators include benzophenone; acetophenone; benzil;benzaldehyde; o-chlorobenzaldehyde; xanthone; thioxanthone;9,10-anthraquinone; 1-hydroxycyclohexyl phenyl ketone;2,2-diethoxyacetophenone; dimethoxyphenylacetophenone; methyldiethanolamine; dimethylaminobenzoate;2-hydroxy-2-methyl-1-phenylpropane-1-one; 2,2-di-sec-butoxyacetophenone;2,2-dimethoxy-1,2-diphenylethan-1-one; dimethoxy-ketal; phenyl glyoxal2,2′-diethoxyacetophenone; hydroxycyclohexyl phenyl ketone;alpha-hydroxyketones; alpha-amino-ketones; alpha and beta naphthylcarbonyl compounds; benzoin ethers such as benzoin methyl ether; benzil;benzil ketals such as benzil dimethyl ketal; acetophenone; fluorenone;2-hydroxy-2-methyl-1-phenylpropan-1-one, and the like. UV initiators ofthis kind are available commercially, e.g., IRGACURE 184 or DEGACURE1173 from Ciba. Thermal initiators are available from DuPont.

As noted above, actinic radiation activated initiators, preferably UVinitiators, can be employed in addition to and/or as an alternative toheat activated initiators. The presence of both a heat activatedinitiator and actinic radiation activated and initiator results in adual cure system or one that provides an optional thermal or optionallight or optional UV initiated cure method. Given the selectivity ofcertain initiators for polymerizing certain monomers, oligomers and/orprepolymers, one can tailor their encapsulation process to effectpolymerization in only one phase as opposed to multiple phases and/orpolymerization of one or more monomers but not all free radicallycurable or polymerizable monomers. Furthermore, given the half-lives ofcertain of the free radical initiators, one is able to better controlthe extent or degree of polymerization so as to prevent too much curetoo early in the encapsulation process. Similarly, one can employdifferent temperatures for different polymerization steps to regulatethe rate of polymerization, again to better control the formation of thecapsule wall and its constituents. For example, in preparing the oilphase oligomer/prepolymer one may use a heat activated initiator at onetemperature and the same or a different initiator at a highertemperature to effect the further polymerization thereof in forming thecapsule wall. Additionally, it is possible to employ three differentpolymerization temperatures in the encapsulation process where thefirst, preferably the lower temperature, is employed to prepare the oilphase (meth)acrylate oligomer/prepolymer. A second higher temperature isemployed to initiate wall formation through polymerization of the oilphase (meth)acrylate oligomer/prepolymer or of the water soluble orwater dispersible (meth)acrylate monomers and/or oligomers, or both.And, a final, yet higher still, temperature to fully cure or polymerizethe capsule wall material. Again, as noted, one may substitute anon-heat activated initiator for the heat activated initiator in any oneor more of these polymerization steps and/or add a non-heat activatedinitiator which is specific for said one or more of the foregoingpolymerization steps.

In a yet further embodiment, for specialized microencapsulationprocesses, the use of initiators, e.g., thioxanthones, phosphine oxides,metallocenes, tertiary aminobenzenes or tertiary aminobenzophenones,which break down into free radicals on exposure to visible light iseffectively used. Such microencapsulation systems however typicallyrequire special handling of the system to prevent prematurepolymerization or oligomerization by appropriate control of lightingconditions.

In general, the initiator will be present in an amount of 0.01 to 10.0weight percent, preferably 0.1 to 6 weight percent, more preferably 0.5to 2.5 weight percent, in any of the water or oil phases, based on thetotal weight of all constituents. Preferably, though, somewhat lowerlevels of UV initiators may be used, e.g., from 0.1-2.5 weight percent,preferably 0.5-1.0 weight percent, UV initiator, based on total weightof the phase in which it is present.

Initiators are available commercially, such as Vazo initiators, whichtypically indicate a decomposition temperature for the initiator.Preferably the initiator is selected to have a decomposition point ofabout 50° C. or higher. Blends of initiators can also be employed andare desirable. Usefully, multiple initiators are employed, either as ablend in the oil phase, or in either of the oil or water phases or both.When a blend or combination of initiators is employed they are selectedso as to stagger the decomposition temperatures to coincide with thevarious steps of the capsule wall formation: e.g., pre-polymerization,wall formation and hardening or polymerizing of the capsule wallmaterial. For example, the oil phase can contain a first initiator thatdecomposes at 55° C. and is selected to promote the oil phase(meth)acrylate oligomer/prepolymer formation, the oil phase may alsocontain a second initiator, one that decomposes at 65° C. which aids inpolymerization of the aforementioned oil phase (meth)acrylateoligomer/prepolymer to initiate forming the capsule wall material.Optionally, a third initiator may be contained in the oil phase orpresent in the water phase that decomposes at 85° C. and whichfacilitates polymerization or full cure of the capsule wall material.The amount of each initiator can be typically as low as 0.1 weightpercent or as high as 10 weight percent.

By proper selection of the initiators and the amount by which they areused and/or the time for which they are exposed to the conditions whichgenerate the free radicals, it is possible to effect control or morecontrol over the wall formation process and, in turn, the thickness andproperties of the capsule wall. For example, one may use little or lessinitiator in the second oil phase composition so as to avoid excessoligomerization or prepolymerization of the oil phase (meth)acrylatemonomers and oligomers. Alternatively and/or in addition thereto, onemay terminate and/or alter the conditions that decompose the initiatorso as to stop or at least slow down the generation of free radicals tolikewise stop the polymerization process.

Although the foregoing discussion is made with respect to heat activatedinitiators, it is to be appreciated that the same properties andcapabilities apply if the initiators or at least one of a combination ofinitiators is actinic radiation activated. Here, initiators that areresponsive to different wavelengths of actinic radiation can be used toprovide the same effect as the use of initiators of differentdecomposition temperatures. Additionally, one may use a combination ofheat activated and actinic radiation activated initiators. As notedabove, one can control the speed of polymerization by controlling therate of free radical generation. This can be attained by raising orlowering the temperature of the reaction mix above or below the 10 hourhalf-life temperature of the heat activated free radical initiator orincreasing or decreasing the intensity of the actinic radiation in thecase of actinic radiation activate free radical initiators. Furthermore,it is to be appreciated that if concern exists for the presence ofexcess initiator following wall formation, one may continue to subjectthe mix or the capsules to those conditions that decompose the excessinitiator until such material is consumed.

While the foregoing has presented a brief outline and description ofthose critical components or ingredients as well as many of the variousco-ingredients and optional ingredients that are typically employed,those skilled in the art will readily appreciate and recognize othercomponents or ingredients that may be employed in addition to thosementioned above, either as an active, reactive or in-active component.For example, other ingredients may be added to help adjust or maintainpH, to prevent agglomeration of the dispersed droplets of the emulsions,to stabilize the emulsions, to inhibit premature polymerization, toaccelerate polymerization, etc. Such ingredients are well known andconventional in the microencapsulation art.

Having described the present process in general and specific terms,attention is now directed to the following specific examples whichdemonstrate the marked benefit of the present process and of themicrocapsules resulting therefrom.

EXAMPLES

A plurality of microencapsulation processes were performed, mostembodying the process of the present disclosure and a few omitting oneor more steps and/or compositions/critical ingredients. Additionally,many of the so formed microcapsules were subjected to a plurality oftests as follows.

Test Methods

Several test methodologies were performed on the microcapsules of thepresent invention pertinent to the utility thereof in variousapplications, most especially in fabric treatment applications. Thesetest methods were for determining free oil, static smudge, leakage andfracture strength and deformation.

Free Oil

The amount of free perfume oil in the water phase was determined by GCanalysis using as an internal standard solution 1 mg/ml dibutylphthalate (DBP)/hexane. Samples were prepared by combining approximately1.5-2 grams (40 drops) of the capsule slurry with 10 ml of theDBP/hexane solution in a 20 ml scintillation vial and capping tightly.The sample was then shaken vigorously several times over 30 minutesbefore being pipetted into an autosampler vial and analyzed by GC usingan HP5890 GC connected to HP Chem Station Software: Column: 5 m×0.32 mmid with 1 μm DB-1 liquid phase, Temp: 50° C. for 1 minute then heat to320° C. @15 deg/min, Injector: 275°., Detector: 325° C., 2 ul injection.The % free oil was calculated by dividing the mg of free perfume oilmeasured by the sample weight (mg) and multiplying by 100.

Static Smudge

Static smudge determines the strength of the perfume microcapsules as afunction of percent capsule breakage. A series of standards wereprepared using dibutylphthalate in either hexane or reagent alcohol asfollows: Reference 1=0.5-1.0 mg; Reference 2=5.0-8.0 mg; Reference3=10.0-15.0 mg. Test samples were prepared by diluting the capsuleslurry to 0.1% solids and measure out 920 μL into a small plasticbeaker. The sample is then filtered using Millipore express filtersunder vacuum (part number HPW02500) and the filter paper allowed to dryfor 30 minutes. Thereafter a drop of distilled water is applied to thetop of the filter apparatus and another clean filter placed on top. Thesample is then placed between 2 bond circles which had been cut using aFiskars Medium Squeeze Punch, model number 12-7436, and the sampleinverted and placed on top of the diaphragm of a Mullen tester: thediaphragm being below the hole. On the Mullen Tester, the sample issubjected to 200 psi pressure for 30 seconds and removed. The sample isthen placed in a clean 20 mL scintillation vial, pinched slightly inorder for solvent to flow freely during extraction. 10 ml of theHexane/DBP Internal standard solution is added to the vial and the vialcapped and shaken well. The sample is allowed to sit for 10 minutes,shaking once at approx. 5 minutes, following which a portion is pipettedinto a GC vial to which 10 mL of Reagent Alcohol/DBP solution is addedand the contents shaken well. The vial is placed in a 70° C. water bathfor 30 minutes and shaken once at approx. the 15 minute mark. After 30minutes the vial is removed from the bath, shaken well, and allowed tocool to room temperature. When cooled, the solution is pipetted into aclean GC vial and analyzed by GC using an HP5890 GC connected to HP ChemStation Software: Column: 5 m×0.32 mm id with 1 μm DB-1 liquid phase,Temp: 50° C. for 1 minute then heat to 320° C. @15 deg/min, Injector:275° C., Detector: 325° C., 2 ul injection. Static Smudge is calculatedby dividing the mg of perfume oil in the hexane by the sum of the mg ofperfume oil in hexane and in the reagent alcohol and multiplying by 100.

Hexane Leakage

The porosity/barrier integrity of the capsule walls was determined bymeasuring the total perfume oil that was extracted into a hexane phaseover periods of 24 hours, 1 week, 2 weeks and 4 weeks. Samples wereprepared by vigorously shaking the microcapsule slurry to ensurehomogeneous mixing of the material and then extracting a predeterminedamount which is then added to a 150 mL jar containing 47 mL ofde-ionized water. 50 mL of a 1 mg/ml dibutylphthalate in hexane solutionis gently added to the aqueous suspensions, without swirling or shaking,and the sample capped tightly. Aliquots were then taken from the upperhexane layer at t=24 hours, 1 week, 2 weeks and 4 weeks and analyzed byGC using an HP5890 GC connected to HP Chem Station Software: Column: 5m×0.32 mm id with 1 μm DB-1 liquid phase, Temp: 50 deg for 1 minute thenheat to 320 deg @15 deg/min, Injector: 275° C., Detector: 325° C., and 2ul injection. Percent leakage was determined by dividing the mg ofperfume oil detected in the hexane by the total theoretical weight ofthe perfume oil, multiplied by 100.

Fracture Strength and Deformation

Fracture strength and deformation of the microcapsules were determinedusing a Hysitron nanoindentation instrument. Samples were prepared bydiluting a drop of the microcapsule slurry in 100 g DI water and thenapplying 2 drops of the diluted slurry to glass slides, spreading theslurry evenly on the slide. The slides were then placed into the Tappiroom for at least four hours before testing to determine both fracturestrength and fracture displacement. Fracture strength, the force neededto rupture the capsules, is determined as 1.27×Fracture force/(Capsulesize)². Fracture displacement, the percent deformation at rupture, isdetermined as fracture displacement/capsule size×100.

Table 1 sets forth the ingredient list of key ingredients employed inthe examples.

TABLE 1 Code Description Captex 355 Medium chain triglyceride based oncaprylic and capric acids CD9055 2-carboxyethylmethacrylate Colloid 121polyacrylic acid emulsifier Colloid 351 copolymer of 92% acrylic acidand 8% butyl acrylate emulsifier CN975 Hexafunctional aromatic urethaneacrylate oligomer Cymel 385 methylated high imino melamine resin with alow degree of alkylation RO/DI Reverse osmosis/deionized water EH EthylHeptanoate IPM Isopropyl myristate - perfume diluent NaOH Sodiumhydroxide (21.5%) NaS sodium sulfate (5%) NaHS Sodium bisulfate (5%) POPeppermint oil SR9035 15 mol ethoxylated trimethylolpropane triacrylateSR444 Pentaerythritol triacrylate SR601 Ethoxylated (4) bisphenol Adiacrylate TBAEMA Tertiary-butylaminoethyl methacrylate V-67/Vazo-2,2′-azobis(2-methylbutyronitrile) - 10 hour 1/2 life at 67 67° C.V-501/Vazo- 4,4′-azobis(4-cyanovaleric acid) - 10 hour 1/2 life at 69°C. 501 V-50 2,2′-Azobis(2-methylpropionamidine)dihydrochloride - 10 hour1/2 life at 56° C. PFO Perfume Oil

Comparative Example 1—MF Single Wall

A first water phase was prepared by combining 17.5 g Colloid 351(copolymer of 92% acrylic acid and 8% butyl acrylate available fromRhone-Poulenc, Cedex, France), 17.5 g Colloid 121 (polyacrylic acidavailable from Rhone-Poulenc, Cedex, France), and 200 g DI water in areactor. The pH was adjusted to 5.9 with 7.4 g of 21.5% aqueous sodiumhydroxide. The mixture was stirred and 7.5 g Cymel 385 (a methylatedhigh imino melamine resin with a low degree of alkylation available fromAllnex Co., Brussels, Belgium) was added dropwise over one minute. Thecore material, a mixture of 120 g peppermint oil and 80 g Captex 355 (atriglyceride manufactured by the esterification of glycerin and fattyacids (mainly caprylic and capric) from Abitec Corp., Columbus, Ohio)was added and the temperature increased to 53° C. and milling begun.Separately, a melamine-containing polymer precursor was prepared bycombining 4 g Colloid 121, 120 g RO water, and 0.3 g 21.5% sodiumhydroxide, the latter to adjust the pH to 5.0 in a glass beaker. 12 gCymel 385 was then added to the mixture while stirring. This mixture wasthen added to the reactor over a period of two minutes after whichsodium sulfate (4.8 g) was added and the temperature increased to 85° C.and the mixture stirred for 8 hours. The mixture was allowed to cool andsamples removed for testing. The results are shown in Table 2.

Example 2—MF/AC Dual Wall

An aqueous solution of 0.6 g Vazo 501 (4,4′-azobis(4-cyanovaleric acidavailable from Dupont Co., Wilmington, Del.), 140 g water and 0.66 g21.5% sodium hydroxide solution (to adjust the pH to 4.6) was added to amicrocapsule slurry formed in accordance with the process of ComparativeExample 1 and heated to 60° C. for thirty minutes. The mixture was thencooled to 50° C. and a mixture of 1.2 g t-butylaminoethyl methacrylate(TBAEMA), 0.7 g concentrated hydrochloric acid (to adjust pH to 2.8), 10g SR 9035 (15 mole ethoxylated trimethylolpropane triacrylate fromSartomer Co.) and 50 g water was added and the temperature was graduallyincreased to 75° C. and the slurry stirred for three hours. The mixturewas allowed to cool and samples removed for testing. The results areshown in Table 2.

TABLE 2 Leakage Fracture 24 1 2 4 % Free % Static Strength % Examplehours week weeks weeks Oil Smudge (Mpa) Deformation CE1 0.14 0.79 1.191.91 0.03 56.90 4.40 55.44 2 0.26 0.88 1.24 1.83 0.08 58.1 6.40 61.07

Comparative Example 3—MF Single Wall

A first water phase was prepared by combining 17.5 g Colloid 351(copolymer of 92% acrylic acid and 8% butyl acrylate available fromRhone-Poulenc, Cedex, France), 17.5 g Colloid 121 (polyacrylic acidavailable from Rhone-Poulenc, Cedex, France), and 200 g DI water in areactor. The pH was adjusted to 5.9 with 8.26 g of 21.5% aqueous sodiumhydroxide. The mixture was stirred and 7.5 g Cymel 385 (a methylatedhigh imino melamine resin with a low degree of alkylation available fromAllnex Co., Brussels, Belgium) was added dropwise over one minute. 200 gof a core material, a perfume oil composition, was added to the reactorand the mixture milled at 1200 rpm at 53° C. for 22 minutes.

Separately, a melamine-containing polymer precursor was prepared bycombining 4 g Colloid 121, 120 g RO water, and 0.51 g 21.5% sodiumhydroxide, the latter to adjust the pH to 5.0 in a class beaker. 12 gCymel 385 was then added to the mixture while stirring. This mixture wasthen added to the reactor over a period of two minutes after whichsodium sulfate (4.8 g) was added and the temperature increased to 85° C.and the mixture stirred for 8 hours. The mixture was allowed to cool andsamples removed for testing. The results are shown in Table 3.

Example 4—MF/AC Dual Wall

An aqueous solution of 0.6 g Vazo 501 (4,4′-azobis(4-cyanovaleric acidavailable from Dupont Co., Wilmington, Del.), 140 g water and 0.62 g21.5% sodium hydroxide solution (to adjust the pH to 4.8) was heated to60° C. for thirty minutes after which and a mixture of 1.2 gt-butylaminoethyl methacrylate (TBAEMA), 0.7 g concentrated hydrochloricacid (to adjust pH to 2.8) was added and then 10 g SR 9035 (15 moleethoxylated trimethylolpropane triacrylate from Sartomer Co.) in 50 gwater was added and mixed for thirty minutes at 60° C. This compositionwas then added to a microcapsule slurry formed in accordance with theprocess of Comparative Example 3 and the slurry cooked at 50° C. for 3hours. The mixture was allowed to cool and samples removed for testing.The results are shown in Table 3.

TABLE 3 % Free % Static Fracture Example Oil Smudge Strength (Mpa) %Deformation CE3 0.03 47.7 9.62 64.18 4 0.14 39.2 12.21 65.10

TABLE 4 Comparative Exam- Exam- Exam- Ingredient Example 5 Example 6 ple7 ple 8 ple 9 Internal Phase EH 19.66 19.63 17.31 16.40 16.40 Captex 35513.10 13.09 11.54 10.94 10.94 Water Phase I C-351 2.87 2.86 2.52 2.392.39 C-121 2.87 2.86 2.52 2.39 2.39 NaOH 0.98 0.98 0.87 0.94 0.94 DI H₂O32.76 32.72 36.07 27.34 27.34 V-50 0.16 0.14 V-501 0.14 0.14 Cymel 3851.23 1.23 2.81 1.03 1.03 Water Phase II C-121 0.66 0.65 0.55 0.55 DI19.66 19.63 16.4 16.4 Cymel 385 1.97 1.96 1.64 1.64 21.5% NaOH 0.05 0.050.04 0.04 Na₂SO₄ 0.79 BKB 3.42 Water Phase III C-351 0.65 5.91 1.09 1.09DI H₂O 19.63 17.31 16.4 16.4 NaOH 0.22 0.22 TBAEMA 0.33 0.29 HEMA 0.330.29 0.27 0.27 SR444 0.98 0.87 0.82 SR601 0.82 CD9055 0.27 0.27 5%NaHSO₄ 0.33 0.29 0.27 0.27 Na₂SO₄ 0.79 0.69 0.66 0.66 Milling Time 30min 25 min 60 min 60 min 60 min Particle Size (μ) 17.43 16.06 14.8 18.2718.7 Free Oil 0 0 0.01 0 0.02 Static Smudge 28.6 45.8 42.5 47.4 66.0 24hour hexane 0.14 0.14 0.30 0.17 0.38 leakage 1 week hexane 0.85 0.821.62 0.97 1.53 leakage 2 weeks hexane 1.61 1.64 3.08 1.95 2.72 leakage 4weeks hexane 2.17 2.98 5.63 3.72 4.85 leakage

Comparative Example 5, Examples 6-9

A series of dual water phase examples were prepared according to thefollowing general procedure. Water Phase I (WPI) is prepared and held at50° C. for 30 minutes. The Internal Phase (IP) core material wasprepared and heated to 35° C. under nitrogen blanket and subsequentlyadded to Water Phase I. This mixture was milled for various time periodsto attain the targeted emulsion size and then the milling blade replacedwith a mixer blade. A second water phase compositions was then added(WPII) with continuous mixing followed by the addition of a third waterphase (WPIII). The mixture was heated to 75° C. over a period 180minutes and then held at that temperature for a period of 4 hours.Thereafter the temperature of the mixture was elevated to 95° C. over aperiod of 60 minutes and held for 6 hours after which the mixture wasallowed to cool to room temperature naturally. The specific compositionsand make-up of these examples (presented as weight percent of the listedcomponents) as well as the milling times and particle sizes arepresented in Table 4. As noted in Table 4, not all examples employed allphase compositions. In those instances, the process was followed withthe exception of the omission of the preparation and addition of thosecompositions.

About 45 minutes before combining the oil and water phases to beginmilling, the first and second oil phase materials were combined andmixed for 10 minutes. Subsequently, the first water phase was added tothe reactor containing the combined oil phases and the mixture milled at50° C. with samples taken every 15 minutes until a targeted ˜18 microndroplet emulsion of the water phase in the oil phase was obtained. Theemulsion was then heated to 75° C. and cooked for 60 minutes after whichthe second water phase was added while maintaining temperature andmixing and the mixture allowed to continue cooking for an additional 160minutes after which time the temperature was raised to 95° C. and themix cooked for an additional 7 hours. Microcapsules prepared by thismethod were then sampled and tested and the results shown in Table 5.

TABLE 5 Leakage Fracture 24 1 2 4 % Free % Static Strength % Examplehours week weeks weeks Oil Smudge (Mpa) Deformation E10 2.16 6.66 9.7616.31 0.13 69.5 2.27 38.52

Comparative Example 11—AC Single Wall

A first oil phase composition was prepared by combining 84.38 g of aperfume oil 75 g IPM, 1 g Vazo 67 and 0.8 g V-501 in a reactor vessel at35° C. under nitrogen blanket with low speed mixing (120 rpm) afterwhich it has heated to 70° C. and held for 45 minutes and then cooledand held at 50° C. A second oil phase composition was separatelyprepared by combining 28.13 g of a perfume, 0.22 g TBAEMA, and 0.22 gCD9055 in a second vessel. To this second oil phase composition wasadded 18 g of CN975 (about 45 minutes prior to forming the emulsion) andthe mixture added to the reactor vessel containing the first oil phasecomposition and mixed for 10 minutes. Thereafter a water phasecomposition prepared by combining 22.5 g C351, 1.2 g V-501, 325 g RO/DIwater and 1.1 g NaOH (21.5%)(added to bring the pH to 4.6) was added tothe combined oil phase composition in the reactor vessel and the mixturemilled, taking samples every 15 minutes until the targeted droplet sizewas attained (16.8 microns). The composition was then heated to 75° C.and held for 5 hours after which the temperature was raised again to 95°C. and held for an additional 7 hours. The mixture was allowed to cooland samples removed for testing. The results are shown in Table 6.

Example 12—AC/MF Dual Wall

A water phase composition was prepared by combining 17.45 g C351, 36 gCymel 385 and 51.42 g RO/DI water and then 4.71 g NaOH (21.5%) to adjustthe pH to 5. This water phase composition was then added to amicrocapsule slurry formed in accordance with the process of ComparativeExample 11 and the slurry cooked at 60° C. for 1 hour. The mixture wasallowed to cool and samples removed for testing. The results are shownin Table 6.

TABLE 6 % Free % Static Fracture Example Oil Smudge Strength (Mpa) %Deformation CE11 0.05 79.3 2.92 36.34 12 0.01 67.3 4.29 45.03

Comparative Example 13, Examples 14-17

A series of dual oil/water phase examples were prepared according to thefollowing general procedure. The components of Oil Phase II (OP II) areadded to a reactor vessel and mixed at low speed (˜120 rpm) at 35° C.under a nitrogen blanket. Oil Phase Ii is then heated to 75° C. over aperiod of 45 minutes and held at that temperature for an additional 45minutes. The components of Oil Phase I, less the multifunctional(meth)acrylate (CN975), is mixed at room temperature and set aside.About 45 minutes prior to milling, the multifunctional (meth)acrylate(CN975) is added and mixed and this mixture then added to the reactorcontaining Oil Phase II and mixed for 10 minutes. Concurrently, theWater Phase I and Water Phase II compositions are individually preparedand heated to 50° C. and held. Water Phase I is added to the oil phasemixture and the contents of the reactor milled for about one hour. Aftermilling, the milling blade is replaced with a mixer blade and WaterPhase II is added. With mixing, the contents of the reactor vessel isthen heated to 75° C. over a period of 180 minutes and then held at thattemperature for a period of 4 hours. Thereafter the temperature of themixture was elevated to 95° C. over a period of 60 minutes and held for6 hours after which the mixture was allowed to cool to room temperaturenaturally. The specific compositions and make-up (presented as weightpercent of the listed components) of these examples are presented inTable 7. As noted in Table 7, not all examples employed all phasecompositions. In those instances, the process was followed with theexception of the omission of the preparation and addition of thosecompositions.

TABLE 7 Comparative Exam- Exam- Exam- Exam- Ingredient Example 13 ple 14ple 15 ple 16 ple 17 Water Phase I C-351 4.01 3.52 3.52 3.52 3.52 21.5%NaOH 0.86 0.75 0.75 0.75 0.75 DI H₂O 57.91 50.88 50.86 50.86 50.88 V-5010.21 0.19 0.19 0.19 0.19 Cymel 385 0.63 Water Phase II C-351 1.25 1.251.25 1.25 DI H₂O 8.05 8.05 8.05 8.05 Cymel 385 1.88 1.88 1.88 1.25 21.5%NaOH 0.21 0.21 0.21 0.21 Na₂SO₄ 0.75 0.75 0.75 0.75 Oil Phase I PO 6.685.87 5.87 5.87 5.87 TBAEMA 0.04 0.03 0.03 0.07 0.03 CD9055 0.04 0.030.07 0.03 0.03 CN975 3.21 2.82 2.82 2.82 2.82 Oil Phase II PO 13.3611.74 11.74 11.74 11.74 Captex 355 13.36 11.74 11.74 11.74 11.74 Vazo 670.18 0.16 0.16 0.16 0.16 V-501 0.14 0.13 0.13 0.13 0.13 Particle Size(μ) 20.3 20.06 20.06 20.06 25.65 Free Oil 0.36 0.04 0.05 0.05 0.04Static Smudge 63.8 60.0 59.3 60.8 87.1 24 hour Hexane 6.62 1.34 2.412.14 0.99 Leakage 1 week Hexane 27.02 13.65 21.28 17.09 3.11 Leakage 2weeks Hexane 32.70 18.64 26.15 22.84 4.48 Leakage 4 weeks Hexane 48.5231.93 41.00 38.27 5.76 Leakage

Of particular note, in the case of Example 17 a portion of the Cymel 385melamine resin was added to both water phase compositions. It was foundthat the addition of the melamine resin to Water Phase I resulted in asignificant reduction in the formation of extraneous particles of themelamine resin. In contrast, those compositions in which the melamineresin was only present in Water Phase II were found to have asignificant amount of small particles (<1μ) of polymerized wallmaterial. Though not intending to be bound by theory, it is alsobelieved that the small amount of Cymel 385 melamine resin in WaterPhase I initiates wall formation at the interface of the oil and waterphases, thereby physically stabilizing the droplets of the oil phase inthe water phase.

Commercial Applications

The microcapsules formed according to the present teachings have anumber of commercial applications. For convenience, before addressingspecific application, the following definitions are presented as theypertain to the discussion on commercial applications.

As used herein “consumer product” means baby care, beauty care, fabric &home care, family care, feminine care, health care, snack and/orbeverage products or devices intended to be used or consumed in the formin which it is sold, and not intended for subsequent commercialmanufacture or modification. Such products include but are not limitedto fine fragrances (e.g. perfumes, colognes eau de toilettes,after-shave lotions, pre-shave, face waters, tonics, and otherfragrance-containing compositions for application directly to the skin),diapers, bibs, wipes; products for and/or methods relating to treatinghair (human, dog, and/or cat), including, bleaching, coloring, dyeing,conditioning, shampooing, styling; deodorants and antiperspirants;personal cleansing; cosmetics; skin care including application ofcreams, lotions, and other topically applied products for consumer use;and shaving products, products for and/or methods relating to treatingfabrics, hard surfaces and any other surfaces in the area of fabric andhome care, including: air care, car care, dishwashing, fabricconditioning (including softening), laundry detergency, laundry andrinse additive and/or care, hard surface cleaning and/or treatment, andother cleaning for consumer or institutional use; products and/ormethods relating to bath tissue, facial tissue, paper handkerchiefs,and/or paper towels; tampons, feminine napkins; products and/or methodsrelating to oral care including toothpastes, tooth gels, tooth rinses,denture adhesives, tooth whitening; over-the-counter health careincluding cough and cold remedies, pain relievers, RX pharmaceuticals,pet health and nutrition, and water purification; processed foodproducts intended primarily for consumption between customary meals oras a meal accompaniment (non-limiting examples include potato chips,tortilla chips, popcorn, pretzels, corn chips, cereal bars, vegetablechips or crisps, snack mixes, party mixes, multigrain chips, snackcrackers, cheese snacks, pork rinds, corn snacks, pellet snacks,extruded snacks and bagel chips); and coffee.

As used herein “cleaning and/or treatment compositions” means productscomprising fluid laundry detergents, fabric enhancers, laundry and/orrinse additives, fluid dishwashing detergents, fluid hard surfacecleaning and/or treatment compositions, fluid toilet bowl cleaners thatmay or may not be contained in a unit dose delivery product all forconsumer, agricultural, industrial or institutional use.

The term “absorbent article” is used herein in a very broad senseincluding any article able to receive and/or absorb and/or containand/or retain fluids and/or exudates, especially bodily fluids/bodilyexudates. Exemplary absorbent articles in the context of the presentinvention are disposable absorbent articles. The term “disposable” isused herein to describe articles, which are not intended to be launderedor otherwise restored or reused as an article (i.e. they are intended tobe discarded after a single use and preferably to be recycled, compostedor otherwise disposed of in an environmentally compatible manner).Typical disposable absorbent articles according to the present inventionare diapers, surgical and wound dressings, breast and perspiration pads,incontinence pads and pants, bed pads as well as absorbent articles forfeminine hygiene like sanitary napkins, panty liners, tampons,interlabial devices or the like. Absorbent articles suitable for use inthe present invention include any type of structures, from a singleabsorbent layer to more complex multi-layer structures. Certainabsorbent articles include a fluid pervious topsheet, a backsheet, whichmay be fluid impervious and/or may be water vapor and/or gas pervious,and an absorbent element comprised there between, often also referred toas “absorbent core” or simply “core”.

The term “Sanitary tissue product” or “tissue product” as used hereinmeans a wiping implement for post-urinary and/or post-bowel movementcleaning (toilet tissue products), for otorhinolaryngological discharges(facial tissue products) and/or multi-functional absorbent and cleaninguses (absorbent towels such as paper towel products and/or wipeproducts). The sanitary tissue products of the present invention maycomprise one or more fibrous structures and/or finished fibrousstructures, traditionally, but not necessarily, comprising cellulosefibers.

The term “tissue-towel paper product” refers to products comprisingpaper tissue or paper towel technology in general, including, but notlimited to, conventional felt-pressed or conventional wet-pressed tissuepaper, pattern densified tissue paper, starch substrates, and high bulk,uncompacted tissue paper. Non-limiting examples of tissue-towel paperproducts include towels, facial tissue, bath tissue, table napkins, andthe like.

“Personal care composition” refers to compositions intended for topicalapplication to skin or hair and can be, for example, in the form of aliquid, semi-liquid cream, lotion, gel, or solid. Examples of personalcare compositions can include, but are not limited to, bar soaps,shampoos, conditioning shampoos, body washes, moisturizing body washes,shower gels, skin cleansers, cleansing milks, in-shower bodymoisturizers, pet shampoos, shaving preparations, etc.

“Bar soap” refers to compositions intended for topical application to asurface such as skin or hair to remove, for example, dirt, oil, and thelike. The bar soaps can be rinse-off formulations, in which the productis applied topically to the skin or hair and then subsequently rinsedwithin minutes from the skin or hair with water. The product could alsobe wiped off using a substrate. Bar soaps can be in the form of a solid(e.g., non-flowing) bar soap intended for topical application to skin.The bar soap can also be in the form of a soft solid which is compliantto the body. The bar soap additionally can be wrapped in a substratewhich remains on the bar during use.

“Rinse-off” means the intended product usage includes application toskin and/or hair followed by rinsing and/or wiping the product from theskin and/or hair within a few seconds to minutes of the applicationstep.

“Ambient” refers to surrounding conditions at about one atmosphere ofpressure, 50% relative humidity and about 25° C.

“Anhydrous” refers to compositions and/or components which aresubstantially free of added or free water.

“Antiperspirant composition” refers to antiperspirant compositions,deodorant compositions, and the like. For example, antiperspirantcreams, gels, soft solid sticks, body sprays, and aerosols.

“Soft solid” refers to a composition with a static yield stress of about200 Pa to about 1,300 Pa. The term “solid” includes granular, powder,bar and tablet product forms.

The term “fluid” includes liquid, gel, paste and gas product forms.

The term “situs” includes paper products, fabrics, garments, hardsurfaces, hair and skin.

The term “substantially free of” refers to about 2% or less, about 1% orless, or about 0.1% or less of a stated ingredient. “Free of” refers tono detectable amount of the stated ingredient or thing.

As used herein, the terms “a” and “an” mean “at least one”.

As used herein, the terms “include”, “includes” and “including” aremeant to be non-limiting.

Unless specifically stated otherwise, the test methods disclosed in theTest Methods Section of the present application should be used todetermine the respective values of the parameters of Applicants'inventions.

Unless otherwise noted, in discussing the commercial applications below,all component or composition levels are in reference to the activeportion of that component or composition, and are exclusive ofimpurities, for example, residual solvents or by-products, which may bepresent in commercially available sources of such components orcompositions.

Similarly, all percentages and ratios are calculated by weight unlessotherwise indicated and are calculated based on the total compositionunless otherwise indicated.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

Consumer Products

A consumer product comprising a consumer product ingredient and animproved dual melamine resin/(meth)acrylate polymer walled microcapsuleswherein the improvement comprises the use of a combination of (a) atleast one oil soluble or dispersible amine (meth)acrylate, (b) at leastone oil soluble or dispersible acidic (meth)acrylate or at least one oilsoluble or dispersible simple acid or both, and (c) at least one oilsoluble or dispersible multifunctional (meth)acrylate monomer oroligomer in forming the (meth)acrylate ester-based portion of themicrocapsule wall, is disclosed. Preferably said consumer productcomprises, based on total consumer product weight from 0.001% about toabout 25%, more preferably from about 0.01% to about 10%, morepreferably from about 0.05% to about 5%, most preferably from about 0.1%to about 0.5% of said microcapsules.

A method of making a consumer product comprising combining a consumerproduct ingredient and a microcapsule made by an improved method ofmaking dual melamine resin/(meth)acrylate polymer walled microcapsuleswherein the improvement comprises the use of a combination of (a) atleast one oil soluble or dispersible acidic (meth)acrylate, (b) at leastone oil soluble or dispersible simple base, and (c) at least one oilsoluble or dispersible multifunctional (meth)acrylate monomer oroligomer in forming the (meth)acrylate ester-based portion of themicrocapsule wall is disclosed.

A method of making a consumer product comprising combining a consumerproduct ingredient and a microcapsule made by an improved method ofmaking dual melamine resin/(meth)acrylate polymer walled microcapsuleswherein the improvement comprises (i) the use of either (A) (a) at leastone oil soluble or dispersible amine (meth)acrylate, (b) at least oneoil soluble or dispersible acidic (meth)acrylate or at least one oilsoluble or dispersible simple acid or both, and (c) at least one oilsoluble or dispersible multifunctional (meth)acrylate monomer oroligomer or (B) a combination of (a) at least one oil soluble ordispersible acidic (meth)acrylate, (b) at least one oil soluble ordispersible simple base, and (c) at least one oil soluble or dispersiblemultifunctional (meth)acrylate monomer or oligomer in forming the(meth)acrylate ester-based portion of the microcapsule wall and (ii) theconcurrent or near concurrent deposition and polymerization of the(meth)acrylate polymer and melamine resin at the oil/water phaseinterface, is disclosed.

A method of making a consumer product comprising combining a consumerproduct ingredient and a microcapsule made by an improved method ofmaking dual melamine resin/(meth)acrylate polymer walled microcapsuleswherein the improvement comprises the use of (a) at least one watersoluble or dispersible multifunctional (meth)acrylate monomer oroligomer alone or in combination with (b) at least one water soluble ordispersible mono- and/or di-functional (meth)acrylate and/or (c) atleast one water soluble or dispersible simple base in the production ofthe (meth)acrylate ester-based portion of the microcapsule wall, isdisclosed.

A method of making a consumer product comprising combining a consumerproduct ingredient and a microcapsule made by an improved method ofmaking dual melamine resin/(meth)acrylate polymer walled microcapsuleswherein the improvement comprises the selected use of water soluble ordispersible melamine resin pre-polymers and/or polymers and/or theprecursors therefore which are able to polymerize/copolymerize throughself-condensation, is disclosed.

Benefit Agents that can Serve as Core Material for Microcapsules

Useful core materials include perfume raw materials, sensates, siliconeoils, waxes, hydrocarbons, higher fatty acids, essential oils, lipids,skin coolants, vitamins, sunscreens, antioxidants, glycerine, catalysts,bleach particles, silicon dioxide particles, malodor reducing agents,odor-controlling materials, chelating agents, antistatic agents,softening agents, insect and moth repelling agents, colorants,antioxidants, chelants, bodying agents, drape and form control agents,smoothness agents, wrinkle control agents, sanitization agents,disinfecting agents, germ control agents, mold control agents, mildewcontrol agents, antiviral agents, drying agents, stain resistanceagents, soil release agents, fabric refreshing agents and freshnessextending agents, chlorine bleach odor control agents, dye fixatives,dye transfer inhibitors, color maintenance agents, optical brighteners,color restoration/rejuvenation agents, anti-fading agents, whitenessenhancers, anti-abrasion agents, wear resistance agents, fabricintegrity agents, anti-wear agents, anti-pilling agents, defoamers andanti-foaming agents, UV protection agents for fabrics and skin, sun fadeinhibitors, anti-allergenic agents, enzymes, water proofing agents,fabric comfort agents, shrinkage resistance agents, stretch resistanceagents, stretch recovery agents, skin care agents, glycerin, and naturalactives such as aloe vera, vitamin E, shea butter, cocoa butter, and thelike, brighteners, antibacterial actives, antiperspirant actives,cationic polymers, dyes and mixtures thereof. In one aspect, saidperfume raw material is selected from the group consisting of alcohols,ketones, aldehydes, esters, ethers, nitriles alkenes. In one aspect thecore material comprises a perfume. In one aspect, said perfume comprisesperfume raw materials selected from the group consisting of alcohols,ketones, aldehydes, esters, ethers, nitriles alkenes and mixturesthereof. In one aspect, said perfume may comprise a perfume raw materialselected from the group consisting of perfume raw materials having aboiling point (B.P.) lower than about 250° C. and a C log P lower thanabout 3, perfume raw materials having a B.P. of greater than about 250°C. and a C log P of greater than about 3, perfume raw materials having aB.P. of greater than about 250° C. and a C log P lower than about 3,perfume raw materials having a B.P. lower than about 250° C. and a C logP greater than about 3 and mixtures thereof. Perfume raw materialshaving a boiling point B.P. lower than about 250° C. and a C log P lowerthan about 3 are known as Quadrant I perfume raw materials, perfume rawmaterials having a B.P. of greater than about 250° C. and a C log P ofgreater than about 3 are known as Quadrant IV perfume raw materials,perfume raw materials having a B.P. of greater than about 250° C. and aC log P lower than about 3 are known as Quadrant II perfume rawmaterials, perfume raw materials having a B.P. lower than about 250° C.and a C log P greater than about 3 are known as a Quadrant III perfumeraw materials. In one aspect, said perfume comprises a perfume rawmaterial having B.P. of lower than about 250° C. In one aspect, saidperfume comprises a perfume raw material selected from the groupconsisting of Quadrant I, II, III perfume raw materials and mixturesthereof. In one aspect, said perfume comprises a Quadrant III perfumeraw material. Suitable Quadrant I, II, III and IV perfume raw materialsare disclosed in U.S. Pat. No. 6,869,923 B1.

In one aspect, said perfume comprises a Quadrant IV perfume rawmaterial. While not being bound by theory, it is believed that suchQuadrant IV perfume raw materials can improve perfume odor “balance”.Said perfume may comprise, based on total perfume weight, less thanabout 30%, less than about 20%, or even less than about 15% of saidQuadrant IV perfume raw material.

Additional Consumer Product Specifics

Additional consumer product specifics are found below. Such disclosureis also intended to cover the process of making the disclosed consumerproducts wherein said process comprises combing the materials asdisclosed to form the described consumer product.

Cleaning and/or Treatment Compositions and Methods of Use

Preferably, said consumer product is a cleaning and/or treatmentcomposition having a viscosity of from about 10 mPa·s to about 50,000mPa·s, preferably from about 50 mPa·s to about 2000 mPa·s, mostpreferably from about 75 mPa·s to about 400 mPa·s, a pH from about 3 toabout 10, preferably from about 4 to about 8, most preferably from about5 to about 8, said composition comprising, based on total cleaningand/or treatment composition weight with from 0.001% about to about 25%,preferably from about 0.01% to about 10%, more preferably from about0.05% to about 5%, most preferably from about 0.1% to about 0.5% of themicrocapsules disclosed here in.

As the viscosity range of the cleaning and/or treatment composition istightened, it is easier to suspend certain materials such as polymersand waxes.

Preferably said cleaning and/or treatment composition comprises:

-   -   (a) a surfactant selected from the group consisting of nonionic        surfactants, anionic surfactants, cationic surfactants,        ampholytic surfactants, zwitterionic surfactants, semi-polar        nonionic surfactants and mixtures thereof;    -   (b) a solvent wherein the solvent is preferably selected from        the group consisting of hydrogenated castor oil, glycols,        alcohols, and mixtures thereof;    -   (c) a fabric softener active wherein the fabric softener active        is preferably selected from the group consisting of a quaternary        ammonium compound, an amine and mixtures thereof, preferably        said quaternary ammonium compound is selected from the group        consisting of bis-(2-hydroxypropyl)-dimethylammonium        methylsulphate fatty acid ester,        1,2-di(acyloxy)-3-trimethylammoniopropane chloride,        N,N-bis(stearoyl-oxy-ethyl) N,N-dimethyl ammonium chloride,        N,N-bis(tallowoyl-oxy-ethyl) N,N-dimethyl ammonium chloride,        N,N-bis(stearoyl-oxy-ethyl) N-(2 hydroxyethyl) N-methyl ammonium        methylsulfate, 1, 2 di-(stearoyl-oxy) 3 trimethyl        ammoniumpropane chloride, dicanoladimethylammonium chloride,        di(hard)tallowdimethylammonium chloride,        dicanoladimethylammonium methylsulfate,        1-methyl-1-stearoylamidoethyl-2-stearoylimidazolinium        methylsulfate, 1-tallowylamidoethyl-2-tallowylimidazoline,        dipalmethyl hydroxyethylammoinum methosulfate and mixtures        thereof, and    -   (d) mixtures of (a) through (c).

Preferably said cleaning and/or treatment composition, comprises anadjunct ingredient selected from the group consisting of builders,chelating agents, dye transfer inhibiting agents, dispersants, enzymes,and enzyme stabilizers, catalytic materials, bleach activators, hydrogenperoxide, sources of hydrogen peroxide, preformed peracids, polymericdispersing agents, clay soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, hueing dyes, perfumes, perfumedelivery systems, structure elasticizing agents, carriers, structurants,hydrotropes, processing aids, solvents in addition to said solubilizingagent, a fabric softener active selected from the group consisting of asilicone polymer, a polysaccharide, a clay, a fatty ester, a dispersiblepolyolefin, a polymer latex and mixtures thereof, pigments, and mixturesthereof, preferably said composition comprises an organic acid,preferably citric acid and/or lactic acid, hydrogenated castor oil,ethoxylated polyethyleneimines, preferably PEI 600 EO 20 and/or PEI 600,an enzyme, preferably a cold water amylase, cold water protease and/orxyloglucanase.

In one aspect of Applicants' cleaning and/or treatment composition, saidcleaning and/or treatment composition comprises a fabric softener activeselected from the group consisting of a quaternary ammonium compound, asilicone polymer, a polysaccharide, a clay, an amine, a fatty ester, adispersible polyolefin, a polymer latex and mixtures thereof, preferably

-   -   (a) said quaternary ammonium compound comprises an alkyl        quaternary ammonium compound, preferably said alkyl quaternary        ammonium compound is selected from the group consisting of a        monoalkyl quaternary ammonium compound, a dialkyl quaternary        ammonium compound, a trialkyl quaternary ammonium compound and        mixtures thereof;    -   (b) said silicone polymer is selected from the group consisting        of cyclic silicones, polydimethylsiloxanes, aminosilicones,        cationic silicones, silicone polyethers, silicone resins,        silicone urethanes, and mixtures thereof;    -   (c) said polysaccharide comprises a cationic starch;    -   (d) said clay comprises a smectite clay;    -   (e) said dispersible polyolefin is selected from the group        consisting of polyethylene, polypropylene and mixtures thereof;        and    -   (f) said fatty ester is selected from the group consisting of a        polyglycerol ester, a sucrose ester, a glycerol ester and        mixtures thereof.

In one aspect of Applicants' cleaning and/or treatment composition, saidcleaning and/or treatment composition comprises a fabric softener activecomprising a material selected from the group consisting ofmonoesterquats, diesterquats, triesterquats, and mixtures thereof,preferably, said monoesterquats and diesterquats are selected from thegroup consisting of bis-(2-hydroxypropyl)-dimethylammonium methylsulfatefatty acid ester and isomers of bis-(2-hydroxypropyl)-dimethylammoniummethylsulfate fatty acid ester and/or mixtures thereof,1,2-di(acyloxy)-3-trimethylammoniopropane chloride,N,N-bis(stearoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride,N,N-bis(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride,N,N-bis(stearoyl-oxy-ethyl)-N-(2-hydroxyethyl)-N-methyl ammoniummethylsulfate, N,N-bis-(stearoyl-2-hydroxypropyl)-N,N-dimethylammoniummethylsulfate, N,N-bis-(tallowoyl-2-hydroxypropyl)-N,N-dimethylammoniummethylsulfate, N,N-bis-(palmitoyl-2-hydroxypropyl)-N,N-dimethylammoniummethylsulfate, N,N-bis-(stearoyl-2-hydroxypropyl)-N,N-dimethylammoniumchloride, 1,2-di-(stearoyl-oxy)-3-trimethyl ammoniumpropane chloride,dicanoladimethylammonium chloride, di(hard)tallowdimethylammoniumchloride, dicanoladimethylammonium methylsulfate,1-methyl-1-stearoylamidoethyl-2-stearoylimidazolinium methylsulfate,1-tallowylamidoethyl-2-tallowylimidazoline, dipalmylmethylhydroxyethylammoinum methylsulfate and mixtures thereof.

In one aspect of Applicants' cleaning and/or treatment composition, saidcomposition comprises a quaternary ammonium compound and a siliconepolymer, preferably said composition comprises from 0.001% to 10%, from0.1% to 8%, more preferably from 0.5% to 5%, of said silicone polymer.

In one aspect of Applicants' cleaning and/or treatment composition, saidfabric softening active has an Iodine Value of between 0-140, preferably5-100, more preferably 10-80, even more preferably, 15-70, mostpreferably 18-25 or when said fabric softening active comprises apartially hydrogenated fatty acid quaternary ammonium compound saidfabric softening active most preferably has a Iodine Value of 25-60.

In one aspect of Applicants' cleaning and/or treatment composition, saidcleaning and/or treatment composition is a soluble unit-dose productsaid soluble unit dose product comprising one or more cleaning and/ortreatment compositions contained within one or more chambers saidchambers being formed from one or more films, preferably said one ormore films comprise PVA film.

The compositions of the present invention may be used in anyconventional manner. In short, they may be used in the same manner asproducts that are designed and produced by conventional methods andprocesses. For example, compositions of the present invention can beused to treat a situs inter alia a surface or fabric. Typically at leasta portion of the situs is contacted with an aspect of Applicants'composition, in neat form or diluted in a wash liquor, and then thesitus is optionally washed and/or rinsed. For purposes of the presentinvention, washing includes but is not limited to, scrubbing, andmechanical agitation. The fabric may comprise any fabric capable ofbeing laundered in normal consumer use conditions. When the wash solventis water, the water temperature typically ranges from about 5° C. toabout 90° C. and, when the situs comprises a fabric, the water to fabricmass ratio is typically from about 1:1 to about 100:1.

The cleaning and/or treatment compositions of the present invention maybe used as liquid fabric enhancers wherein they are applied to a fabricand the fabric is then dried via line drying and/or drying the anautomatic dryer.

In one aspect, a method of controlling malodors comprising: contacting asitus comprising a malodor and/or a situs that will become malodorouswith a cleaning and/or treatment composition selected from the groupconsisting of Applicants' cleaning and/or treatment compositions andmixtures thereof, is disclosed.

In one aspect of Applicants' method, said situs comprises a fabric andsaid contacting step comprises contacting said fabric with a sufficientamount of Applicants' cleaning and/or treatment compositions to providesaid fabric with at least 0.0025 mg of benefit agent, such as perfume,per kg of fabric, preferably from about 0.0025 mg of benefit agent/kg offabric to about 50 mg of malodor reduction material/kg of fabric, morepreferably from about 0.25 mg of benefit agent/kg of fabric to about 25mg of benefit agent/kg of fabric, most preferably from about 0.5 ofbenefit agent/kg of fabric to about 10 mg of benefit agent/kg of fabricof said sum of malodor reduction materials.

Solid Consumer Products and Methods of Use

Preferably said consumer product is a powder, granule, flake, bar orbead, said consumer product comprising, based on total product weight:

-   -   (a) with from 0.001% about to about 25%, preferably from about        0.01% to about 10%, more preferably from about 0.05% to about        5%, most preferably from about 0.1% to about 0.5% of the        microcapsules disclosed here in;    -   (b) a carrier that is a solid at 25° C., preferably said solid        carrier is selected from the group consisting of clays, sugars,        salts, silicates, zeolites, citric acid, maleic acid, succinic        acid, benzoic acid, urea and polyethylene oxide and mixtures        thereof; preferably said carriers is present at a level of:        -   (i) from about 20% to about 95%, more preferably about 30%            to about 90%, even more preferably about 45% to about 90%,            and most preferably about 60% to about 88%; or        -   (ii) from about 1% to about 60%, more preferably about 2% to            about 50%, even more preferably about 3% to about 45% and            most preferably, about 4% to about 40%; and    -   (c) optionally, 0.5% to about 50% of an enzyme stable polymer,        preferably said enzyme stable polymer is selected from the group        consisting of polyacrylate polymers, polyamine polymer,        acrylate/maleate copolymer, a polysaccharide, and mixtures        thereof, preferably said polysaccharide is selected from the        group consisting of carboxy methyl cellulose, cationic hydroxy        ethyl cellulose and mixtures thereof.

In one aspect of said product, said product comprises a perfume.

In one aspect of said product, said product comprising an additionalmaterial that is an adjunct ingredient selected from the groupconsisting of surfactants, builders, chelating agents, dye transferinhibiting agents, dispersants, enzymes, and enzyme stabilizers,catalytic materials, bleach activators, a fabric softener active,hydrogen peroxide, sources of hydrogen peroxide, preformed peracids,polymeric dispersing agents, clay soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, hueing dyes, perfumes, perfumedelivery systems, structure elasticizing agents, carriers, structurants,hydrotropes, processing aids, solvents, pigments and mixtures thereof.

The compositions of the present invention may be used in anyconventional manner. In short, they may be used in the same manner asproducts that are designed and produced by conventional methods andprocesses. For example, compositions of the present invention can beused to treat a situs inter alia a surface or fabric. Typically at leasta portion of the situs is contacted with an aspect of Applicants'composition, in neat form or diluted in a wash liquor, and then thesitus is optionally washed and/or rinsed. For purposes of the presentinvention, washing includes but is not limited to, scrubbing, andmechanical agitation. The fabric may comprise any fabric capable ofbeing laundered in normal consumer use conditions. When the wash solventis water, the water temperature typically ranges from about 5° C. toabout 90° C. and, when the situs comprises a fabric, the water to fabricmass ratio is typically from about 1:1 to about 100:1.

The compositions of the present invention may be used as fabricenhancers wherein they are applied to a fabric and the fabric is thendried via line drying and/or drying the an automatic dryer.

A method of freshening comprising: contacting a situs comprising with aproduct selected from the group consisting of the products describedherein and mixtures thereof, is disclosed.

Freshening Compositions, Methods of Use and Delivery Systems

Preferably, said consumer product is a freshening composition having aviscosity of from about 1 mPa·s to about 50,000 mPa·s, preferably fromabout 1 mPa·s to about 2000 mPa·s, most preferably from about 1 mPa·s toabout 400 mPa·s, a pH from about 3 to about 10, preferably from about 4to about 8, most preferably from about 5 to about 8, said fresheningcomposition comprising, based on total freshening composition weight:

-   -   (a) with from 0.001% about to about 25%, preferably from about        0.01% to about 10%, more preferably from about 0.05% to about        5%, most preferably from about 0.1% to about 0.5% of the        microcapsules disclosed here in; and    -   (b) from about 0.01% to about 3%, preferably from about 0.4% to        about 1%, more preferably from about 0.1% to about 0.5%, most        preferably from about 0.1% to about 0.3% of solubilizing agent,        preferably said solubilizing agent is selected from the group        consisting of a surfactant, a solvent and mixtures thereof,        -   (i) preferably said surfactant comprises a non-ionic            surfactant;        -   (ii) preferably said solvent comprises an alcohol, a polyol            and mixtures thereof;    -   (c) optionally, an adjunct ingredient.

As the viscosity is lowered you obtain improved spray-ability andimproved penetration into fabric.

In one aspect of said freshening composition, said composition comprisesan adjunct ingredient selected from the group consisting of isoalkanescomprising at least 12 carbon atoms, a compound comprising a quaternaryamine moiety, lubricants, additional solvents, glycols, alcohols,silicones, preservatives, anti-microbial agents, pH modifiers, acarrier, insect repellants, metallic salts, cyclodextrins, functionalpolymers, anti-foaming agents, antioxidants, oxidizing agents, chelantsand mixtures thereof; preferably lubricants wherein the lubricantspreferably comprise hydrocarbons, more preferably hydrocarbons thatcomprise two or more branches or compounds comprising a quaternary aminemoiety comprising at least 10 carbon atoms.

A device comprising Applicants' freshening compositions, said devicebeing preferably selected from the group consisting of trigger sprayers,manual aerosol sprayers, automatic aerosol sprayers, wick containingdevices, fan devices, and thermal drop-on-demand devices, is disclosed.

A method of freshening comprising: contacting a situs with a compositionselected from the group consisting of the freshening compositionsdisclosed herein and mixtures thereof is disclosed.

In one aspect of said method, said contacting step comprises contactingsaid situs with a sufficient amount of the compositions disclosed hereinto provide said situs with, from about 0.1 milligrams (mg) to about10,000 mg, preferably from about 1 mg to about 5,000 mg most preferablyfrom about 5 mg to about 1000 mg of a benefit agent, preferably aperfume, per square meter of projected surface area of said situs.

The composition of the present invention may be used with a hard surfacecleaner, as is commonly used to clean countertops, tables and floors. Asuitable floor cleaning liquid is sold by the instant assignee in areplaceable reservoir under the name WetJet. The cleaning solution mayparticularly be made according to the teachings of commonly assignedU.S. Pat. No. 6,814,088. The reservoir may be used with and dispensedfrom a floor cleaning implement, in conjunction with a disposable floorsheet. A suitable spray implement is also sold under the name WetJet. Asuitable reservoir and fitment therefore may be made according to theteachings of commonly assigned U.S. Pat. Nos. 6,386,392 and/or7,172,099. If desired the floor cleaning implement may dispense steam,according to the teachings of jointly assigned US 2013/0319463.Alternatively a refillable reservoir may be utilized.

If desired the composition of the present invention may be used with apre-moistened sheet. If the cleaning sheet is pre-moistened, it ispreferably pre-moistened with a liquid which provides for cleaning ofthe target surface, such as a floor, but yet does not require apost-cleaning rinsing operation. The cleaning sheet may be loaded withat least 1, 1.5 or 2 grams of cleaning solution per gram of drysubstrate, but typically not more than 5 grams per gram. The cleaningsolution may comprise a surfactant, such as APG surfactant whichminimizes streaking since there is typically not a rinsing operation,according to the teachings of U.S. Pat. No. 6,716,805.

The composition of the present invention may be used for raised hardsurfaces, as is sold under the names Mr. Clean and Mr. Proper. Thecomposition may be dispensed from a trigger sprayer or aerosol sprayer,as are well known in the art. An aerosol sprayer dispenses thecomposition using propellant pressure, while a trigger sprayer dispensesthe composition by pumping the composition under manual actuation. Asuitable aerosol dispenser may have a dip tube or bag on valve,according to US 2015/0108163 and/or US 2011/0303766. A suitable triggersprayer is found in U.S. Pat. No. 8,322,631.

The present freshening composition may be used in a device for thedelivery of a volatile material to the atmosphere or on inanimatesurfaces (e.g. fabric surfaces as a fabric refresher). Such device maybe configured in a variety of ways. For example, the device may beconfigured for use as an energized air freshener (i.e. powered byelectricity; or chemical reactions, such as catalyst fuel systems; orsolar powered; or the like). Exemplary energized air freshening devicesinclude a powered delivery assistance means which may include a heatingelement, fan assembly, or the like. More particularly, the device may bean electrical wall-plug air freshener as described in U.S. 7,223,361; abattery (including rechargeable battery) powered air freshener having aheating and/or fan element. In energized devices, the volatile materialdelivery engine may be placed next to the powered delivery assistancemeans to diffuse the volatile perfume material. The volatile perfumematerial may be formulated to optimally diffuse with the deliveryassistance means.

Alternatively, the device may be configured for use as a non-energizedair freshener. An exemplary non-energized air freshener includes areservoir and, optionally, capillary or wicking means or an emanatingsurface, to help volatile materials passively diffuse into the air (i.e.without an energized means). A more specific example includes a deliveryengine having a liquid reservoir for containing a volatile material anda microporous membrane enclosing the liquid reservoir as disclosed inU.S. Pat. No. 8,709,337 and U.S. Pat. No. 8,931,711.

The device may also be configured for use as an aerosol sprayer or anon-aerosol air sprayer including traditional trigger sprayers as wellas trigger sprayer having a pre-compression and/or buffer system forfluid therein. In this embodiment, the delivery engine can delivervolatile materials upon user demand or programmed to automaticallydeliver volatile materials to the atmosphere.

The apparatus may also be configured for use with an air purifyingsystem to deliver both purified air and volatile materials to theatmosphere. Non-limiting examples include air purifying systems usingionization and/or filtration technology for use in small spaces (e.g.bedrooms, bathrooms, automobiles, etc.), and whole house central airconditioning/heating systems (e.g. HVAC).

Article and Method of Use

Preferably said consumer product is an article comprising

-   -   (a) a substrate, preferably a flexible substrate, more        preferably a flexible substrate that is a sheet; preferably said        substrate comprises a fabric softening active, preferably said        fabric softening active coats all or a portion of said        substrate; and    -   (b) based on total article weight with from 0.001% about to        about 25%, preferably from about 0.01% to about 10%, more        preferably from about 0.05% to about 5%, most preferably from        about 0.1% to about 0.5% of the microcapsules disclosed here in.

Preferably said article has a weight ratio of fabric softener active todry substrate ranging from about 10:1 to about 0.5:1, preferably fromabout 5:1 to about 1:1, preferably said fabric softener active isselected from the group consisting of a quaternary ammonium compound, asilicone polymer, a polysaccharide, a clay, an amine, a fatty ester, adispersible polyolefin, a polymer latex and mixtures thereof.

In one aspect, said article has a weight ratio of fabric softener activeto dry substrate ranging from about 10:1 to about 0.5:1, preferably fromabout 5:1 to about 1:1, preferably said fabric softener active isselected from the group consisting of

-   -   (a) a cationic fabric softener active, preferably a        quaternary-ammonium fabric softener active, more preferably a        di(long alkyl chain)dimethylammonium (C₁-C₄ alkyl) sulfate or        chloride, preferably the methyl sulfate; an ester quaternary        ammonium compound, an ester amine precursor of an ester        quaternary ammonium compound, and mixtures thereof, preferably a        diester quaternary ammonium salt;    -   (b) a carboxylic acid salt of a tertiary amine and/or ester        amine;    -   (c) a nonionic fabric softener material, preferably fatty acid        partial esters of polyhydric alcohols, or anhydrides thereof,        wherein the alcohol or anhydride contains from about 2 to about        18 and preferably from about 2 to about 8 carbon atoms, and each        fatty acid moiety contains from about 8 to about 30 and        preferably from about 12 to about 20 carbon atoms;    -   (d) alkanolamides;    -   (e) fatty acids; and    -   (f) mixtures of the foregoing.

Preferably, said article comprises, based on total article weight, from1% to 99% by weight, preferably from about 1% to about 80%, morepreferably from about 20% to about 70%, most preferably from about 25%to about 60% of a fabric softening active.

Preferably said article comprises a quaternary ammonium compoundselected from the group consisting ofbis-(2-hydroxypropyl)-dimethylammonium methylsulphate fatty acid ester,1,2-di(acyloxy)-3-trimethylammoniopropane chloride,N,N-bis(stearoyl-oxy-ethyl) N,N-dimethyl ammonium chloride,N,N-bis(tallowoyl-oxy-ethyl) N,N-dimethyl ammonium chloride,N,N-bis(stearoyl-oxy-ethyl) N-(2 hydroxyethyl) N-methyl ammoniummethylsulfate, 1, 2 di (stearoyl-oxy) 3 trimethyl ammoniumpropanechloride, dicanoladimethylammonium chloride,di(hard)tallowdimethylammonium chloride, dicanoladimethylammoniummethylsulfate, 1-methyl-1-stearoylamidoethyl-2-stearoylimidazoliniummethylsulfate, 1-tallowylamidoethyl-2-tallowylimidazoline, dipalmethylhydroxyethylammoinum methosulfate and mixtures thereof.

In one aspect of said article, said article comprises a fabric softeningactive having an Iodine Value of between 0-140, preferably 5-100, morepreferably 10-80, even more preferably, 15-70, most preferably 18-25.

In one aspect of said article, said article comprises an adjunctingredient selected from the group consisting of surfactants, builders,chelating agents, dye transfer inhibiting agents, dispersants, enzymes,and enzyme stabilizers, catalytic materials, bleach activators, hydrogenperoxide, sources of hydrogen peroxide, preformed peracids, polymericdispersing agents, clay soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, hueing dyes, perfumes, perfumedelivery systems, structure elasticizing agents, carriers, structurants,hydrotropes, processing aids, solvents, pigments anti-oxidants,colorants, preservatives, optical brighteners, opacifiers, stabilizerssuch as guar gum and polyethylene glycol, anti-shrinkage agents,anti-wrinkle agents, soil release agents, fabric crisping agents,reductive agents, spotting agents, germicides, fungicides,anti-corrosion agents, antifoam agents, Color Care Agents includingChlorine Scavangers, Dye Transfer Inhibitors, Dye Fixatives Chelants andAnti-Abrasion Agents Perfume, PMC's, Cyclodextrin Perfume Complexes,Free Cyclodextrin, Pro-Perfumes; Antioxidants and mixtures thereof.

A method of controlling softening and/or freshening comprising:contacting a situs comprising one or more of the articles Applicants'disclose herein, is disclosed.

In one aspect of said method, said situs comprises a fabric and saidcontacting step comprises contacting said fabric with a sufficientamount of Applicants' article containing to provide said fabric with alevel of perfume of at least 0.0025 mg of perfume/kg of fabric,preferably from about 0.00025 mg of perfume/kg of fabric to about 25 mgof perfume/kg of fabric, more preferably from about 0.025 mg ofperfume/kg of fabric to about 20 mg of perfume/kg of fabric, mostpreferably from about 0.25 of perfume/kg of fabric to about 10 mg ofmalodor reduction material/kg of fabric of said sum of malodor reductionmaterials.

One aspect of the present invention relates to fabric conditioningcompositions which are delivered to fabric via dryer-added substratethat effectively releases the composition in an automatic laundry(clothes) dryer. Such dispensing means can be designed for single usageor for multiple uses. The dispensing means can also be a “carriermaterial” that releases the fabric conditioning composition and then isdispersed and/or exhausted from the dryer. When the dispensing means isa flexible substrate, e.g., in sheet configuration, the fabricconditioning composition is releasably affixed on the substrate toprovide a weight ratio of conditioning composition to dry substrateranging from about 10:1 to about 0.5:1, preferably from about 5:1 toabout 1:1. To insure release, preferred flexible sheets withstand thedryer environment without decomposing or changing shape, e.g.combusting, creating off odors, or shrinking with heat or moisture.Substrates especially useful herein are rayon and/or polyester non-wovenfabrics.

Non-limiting examples of the substrates useful herein are cellulosicrayon and/or polyester non-woven fabrics having basis weights of fromabout 0.4 oz./yd² to about 1 oz./yd², preferably from about 0.5 oz./yd²to about 0.8 oz./yd², more preferably from about 0.5 oz./yd² to about0.6 oz./yd². These substrates are typically prepared using, e.g., rayonand/or polyester fibers having deniers of from about 1 to about 8,preferably from about 3 to about 6, and more preferably about 4 to 6 ormixtures of different deniers. Typically, the fiber is a continuousfilament or a 3/16 inch to 2 inch fiber segment that is laid down, in apattern that results in a multiplicity of layers and intersectionsbetween overlayed portions of the filament or fiber, on a belt,preferably foraminous, and then the fiber intersections are glued and/orfused into fiber-to-fiber bonds by a combination of an adhesive binder,and/or heat and/or pressure. As non-limiting examples, the substrate maybe spun-bonded, melt-bonded, or point bonded or combinations of bondingprocesses may be chosen. The substrate breaking strength and elasticityin the machine and cross direction is sufficient to enable the substrateto be conveyed through a coating process. The porosity of the substratearticle is sufficient to enable air flow through the substrate topromote conditioning active release and prevent dryer vent blinding. Thesubstrate may also have a plurality of rectilinear slits extended alongone dimension of the substrate.

The dispensing means will normally carry an effective amount of fabricconditioning composition. Such effective amount typically providessufficient softness, antistatic effect and/or perfume deposition for atleast one treatment of a minimum load in an automatic laundry dryer.Amounts of the fabric conditioning composition irrespective of load sizefor a single article can vary from about 0.1 g to about 100 g,preferably from about 0.1 g to about 20 g, most preferably from about0.1 g to about 10 g. Amounts of fabric treatment composition formultiple uses, e.g., up to about 30, can be used.

Absorbent Article, Polybag or Paper Carton and Methods of Use

Preferably said consumer product is an article selected from anabsorbent article, polybag or paper carton, said article comprising,based on total article weight, with from 0.001% about to about 25%,preferably from about 0.01% to about 10%, more preferably from about0.05% to about 5%, most preferably from about 0.1% to about 0.5% of themicrocapsules of the present invention.

Preferably said article is an absorbent article, preferably saidabsorbent article is a sanitary paper product, said sanitary paperproduct comprising one or more layers of conventional felt-pressedtissue paper, conventional wet-pressed tissue paper, pattern densifiedtissue paper, starch substrates, high bulk, un-compacted tissue paperand mixtures thereof.

Preferably said absorbent article comprises an absorbent core, andoptionally a backsheet, topsheet, acquisition layer or outer wrapper,wherein said microcapsules are disposed on the absorbent core or betweenone or more of the optional layers.

In one aspect of said article, said absorbent article is contained in apolybag or paper carton.

In one aspect of said article, said microcapsules are disposed on saidpolybag or paper carton, and/or on said absorbent article.

Preferably said article is an absorbent article comprises a lotion.

Preferably, said absorbent article comprises one or more adjunctingredients selected from the group consisting of surfactants, inks,dyes, mineral oils, petrolatum, polysiloxanes, cyclodextrins, clays,silicates, aluminates, vitamins, isoflavones, flavones, metal oxides,short chain organic acids (C₁-C₈), triglycerides (C₈-C₂₂), andantioxidants.

In one aspect, a method of providing a benefit agent, preferablyperfume, comprising: incorporating said microcapsules in or on anarticle, preferably an absorbent article, polybag and/or paper carton,is disclosed.

A non-limiting list of suppliers of suitable absorbent articles,polybags, and cartons that can be used in the manufacture of Applicants'articles is as follows: Procter & Gamble of Cincinnati, Ohio, USA;International Paper Products of Memphis, Tenn. USA; and Kimberly Clark,of Irving, Tex., USA. Suitable equipment and processes for makingabsorbent articles can be obtained from Fameccanica Group of Pescara,Italy. Suitable equipment and processes for adding the malodor reductionmaterials to said articles can be obtained from Nordson of Duluth Ga.,USA.

Personal Care Compositions and Methods of Use

Preferably said consumer product is a personal care compositioncomprising, based on total composition weight,

-   -   (a) with from 0.001% about to about 10%, preferably from about        0.1% to about 5%, more preferably from about 0.5% to about 4%,        most preferably from about 1% to about 3% of the microcapsules        disclosed here in;    -   (b) from about 0.1% to about 99%, preferably from about 1% to        about 80%, more preferably from about 5% to about 70%, most        preferably from about 10% to about 50% of a solvent, preferably        said solvent is selected from, water, glycerin, and mixtures        thereof; and    -   (c) from about 0% to about 50%, preferably from about 0% to        about 40%, more preferably from about 0.1% to about 30%, most        preferably from about 0.1% to about 15% of a material selected        from the group consisting of a structurant, a humectant, a        surfactant, an antimicrobial, and mixtures thereof.

Preferably, said personal care composition comprises one or more neatperfume raw materials—the total of said neat perfume raw materials beingthe sum of such neat perfume raw materials based on weight of each neatperfume raw materials.

Preferably, said sum total of neat perfume raw materials has an averageLog P, based on weight percent of each perfume raw material in said sumtotal of neat perfume raw materials, of from about 2.5 to about 8,preferably from about 3 to about 8, more preferably from about 3.5 toabout 7, most preferably, each of said neat perfume raw materials insaid sum total of neat perfume raw materials. This range of Log P willallow the perfume to deposit on the skin and not wash away in the waterphase during use

Preferably said personal care composition, comprises less than 10%,preferably less than 5%, more preferably less than 1% of said one ormore perfume raw materials, based on total combined weight of said oneor more perfume raw materials comprise an ionone moiety.

Preferably said personal care composition comprises a total of, based ontotal personal care composition weight, of from about 3% to 30% of asurfactant, and, optionally, a miscellar phase and/or lamellar phase.

Preferably said personal care composition, said composition comprises atotal, based on total personal care composition weight, of from about0.1% to about 50% of a material selected from structurants, humectants,fatty acids, inorganic salts, antimicrobial agents, antimicrobial agentsactives and mixtures thereof.

Preferably said personal care composition comprises an adjunctingredient selected from the group consisting of clay mineral powders,pearl pigments, organic powders, emulsifiers, distributing agents,pharmaceutical active, topical active, preservatives, surfactants andmixtures thereof.

A method of freshening comprising: contacting a situs with a personalcare composition selected from the group consisting of the personal carecompositions disclosed herein is disclosed.

In one aspect of said method, said situs comprises the body or head ofhair and said contacting step comprises contacting said body or haircontaining a malodor with a sufficient amount of Applicants' personalcare composition to provide said body or hair with a level ofencapsulated benefit agent, preferably perfume, of at least 0.0001 mg ofencapsulated benefit agent per body or head of hair, preferably fromabout 0.0001 mg of encapsulated benefit agent per body or head of hairto about 1 mg of encapsulated benefit agent per body or head of hair,more preferably from about 0.001 mg of encapsulated benefit agent perbody or head of hair about 0.5 mg of encapsulated benefit agent per bodyor head of hair, most preferably from about 0.01 of encapsulated benefitagent per body or head of hair to about 0.2 mg of encapsulated benefitagent per body or head of hair.

Antiperspirant and/or Deodorant Compositions and Methods of Use

Preferably said consumer product is an antiperspirant and/or deodorantcomposition comprising, based on total composition weight,

-   -   (a) with from 0.001% about to about 10%, preferably from about        0.1% to about 5%, more preferably from about 0.5% to about 4%,        most preferably from about 1% to about 3% of the microcapsules        disclosed here in;    -   (b) from about 0.1% to about 99%, preferably from about 1% to        about 80%, more preferably from about 5% to about 55%, most        preferably from about 10% to about 50% of a solvent, preferably        said solvent is selected from cyclopentasiloxane, ethanol,        water, propylene glycol, dipropylene glycol, and mixtures        thereof;    -   (c) from about 0% to about 30%, preferably from about 0% to        about 20%, more preferably from about 0.1% to about 4%, most        preferably from about 0.1% to about 4% of a material selected        from the group consisting of a structurant, a residue masker, an        antimicrobial, and mixtures thereof    -   is disclosed. The aforementioned solvent levels help disperse        perfume into the APDO base to give even coverage when used

Preferably said antiperspirant and/or deodorant composition, comprisesone or more perfume raw materials.

Preferably each of said one or more perfume raw materials has a boilingpoint of from about 160° C. to about 400° C., preferably from about 180°C. to about 400° C.

Preferably less than 10%, preferably less than 5%, more preferably lessthan 1% of said one or more perfume raw materials, based on totalcombined weight of said one or more-perfume raw materials comprise anionone moiety.

Preferably, said antiperspirant and/or deodorant composition is anantiperspirant composition that comprises a total of, based on totalantiperspirant composition weight, from about 1% to about 25% of analuminum salt antiperspirant active.

Preferably said antiperspirant and/or deodorant composition, is ananhydrous antiperspirant composition, said anhydrous antiperspirantcomposition comprising a total of, based on total anhydrousantiperspirant composition weight, from about 1% to about 25% of anantiperspirant actives selected from the group consisting of astringentmetallic salts, preferably inorganic and organic salts of aluminum,zirconium and zinc, as well as mixtures thereof, more preferablyaluminum halides, aluminum chlorohydrate, aluminum hydroxyhalides,zirconyl oxyhalides, zirconyl hydroxyhalides, and mixtures thereof.

Preferably said antiperspirant and/or deodorant composition comprises anadjunct ingredient selected from the group consisting of clay mineralpowders, pearl pigments, organic powders, emulsifiers, distributingagents, pharmaceutical active, topical active, preservatives,surfactants and mixtures thereof.

A method of controlling malodors comprising: contacting a situscomprising a malodor and/or a situs that may become malodorous with anantiperspirant or deodorant composition selected from the groupconsisting of the antiperspirant and/or deodorant composition disclosedherein, is disclosed.

In one aspect of said method, said situs is an underarm and saidcontacting step comprises contacting said underarm with a sufficientamount of Applicants' antiperspirant and/or deodorant compositioncontaining said sum of malodor reduction materials to provide saidunderarm with a level of malodor reduction materials of at least 0.0001mg of malodor reduction material per underarm, preferably from about0.0001 mg of malodor reduction material per underarm to about 10 mg ofmalodor reduction material per underarm, more preferably from about0.001 mg of malodor reduction material per underarm about 5 mg ofmalodor reduction material per underarm, most preferably from about 0.01of malodor reduction material per underarm to about 0.2 mg of malodorreduction material per underarm.

Antiperspirant Compositions

Antiperspirant compositions can be formulated in many forms. For examplean antiperspirant composition can be, without limitation, a roll onproduct, a body spray, a stick including soft solid sticks and invisiblesolids, or an aerosol. Each of the antiperspirant compositions describedbelow can include perfume materials as described herein.

A. Roll-on and Clear Gel

A roll-on antiperspirant composition can comprise, for example, water,emollient, solubilizer, deodorant actives, antioxidants, preservatives,or combinations thereof. A clear gel antiperspirant composition cancomprise, for example, water, emollient, solubilizer, deodorant actives,antioxidants, preservatives, ethanol, or combinations thereof.

-   -   Water—The roll-on composition can include water. Water can be        present in an amount of about 1% to about 99.5%, about 25% to        about 99.5%, about 50% to about 99.5%, about 75% to about 99.5%        about 80% to about 99.5%, from about 15% to about 45%, or any        combination of the end points and points encompassed within the        ranges, by weight of the deodorant composition.    -   Emollients—Roll-on compositions can comprise an emollient system        including at least one emollient, but it could also be a        combination of emollients. Suitable emollients are often liquid        under ambient conditions. Depending on the type of product form        desired, concentrations of the emollient(s) in the deodorant        compositions can range from about 1% to about 95%, from about 5%        to about 95%, from about 15% to about 75%, from about 1% to        about 10%, from about 15% to about 45%, or from about 1% to        about 30%, by weight of the deodorant composition.    -   Emollients suitable for use in the roll-on compositions include,        but are not limited to, propylene glycol, polypropylene glycol        (like dipropylene glycol, tripropylene glycol, etc.), diethylene        glycol, triethylene glycol, PEG-4, PEG-8, 1,2 pentanediol, 1,2        hexanediol, hexylene glycol, glycerin, C2 to C20 monohydric        alcohols, C2 to C40 dihydric or polyhydric alcohols, alkyl        ethers of polyhydric and monohydric alcohols, volatile silicone        emollients such as cyclopentasiloxane, nonvolatile silicone        emollients such as dimethicone, mineral oils, polydecenes,        petrolatum, and combinations thereof. One example of a suitable        emollient comprises PPG-15 stearyl ether. Other examples of        suitable emollients include dipropylene glycol and propylene        glycol.    -   Deodorant Actives—Suitable deodorant actives can include any        topical material that is known or otherwise effective in        preventing or eliminating malodor associated with perspiration.        Suitable deodorant actives may be selected from the group        consisting of antimicrobial agents (e.g., bacteriocides,        fungicides), malodor-absorbing material, and combinations        thereof. For example, antimicrobial agents may comprise        cetyltrimethylammonium bromide, cetyl pyridinium chloride,        benzethonium chloride, diisobutyl phenoxy ethoxy ethyl dimethyl        benzyl ammonium chloride, sodium N-lauryl sarcosine, sodium        N-palmethyl sarcosine, lauroyl sarcosine, N-myristoyl glycine,        potassium N-lauryl sarcosine, trimethyl ammonium chloride,        sodium aluminum chlorohydroxy lactate, triethyl citrate,        tricetylmethyl ammonium chloride, 2,4,4′-trichloro-2′-hydroxy        diphenyl ether (triclosan), 3,4,4′-trichlorocarbanilide        (triclocarban), diaminoalkyl amides such as L-lysine hexadecyl        amide, heavy metal salts of citrate, salicylate, and piroctose,        especially zinc salts, and acids thereof, heavy metal salts of        pyrithione, especially zinc pyrithione, zinc phenolsulfate,        farnesol, and combinations thereof. The concentration of the        optional deodorant active may range from about 0.001%, from        about 0.01%, of from about 0.1%, by weight of the composition to        about 20%, to about 10%, to about 5%, or to about 1%, by weight        of the composition.    -   Odor Entrappers—The composition can include an odor entrapper.        Suitable odor entrappers for use herein include, for example,        solubilized, water-soluble, uncomplexed cyclodextrin. As used        herein, the term “cyclodextrin” includes any of the known        cyclodextrins such as unsubstituted cyclodextrins containing        from six to twelve glucose units, especially,        alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or        their derivatives and/or mixtures thereof. The        alpha-cyclodextrin consists of six glucose units, the        beta-cyclodextrin consists of seven glucose units, and the        gamma-cyclodextrin consists of eight glucose units arranged in a        donut-shaped ring. The specific coupling and conformation of the        glucose units give the cyclodextrins a rigid, conical molecular        structure with a hollow interior of a specific volume. The        “lining” of the internal cavity is formed by hydrogen atoms and        glycosidic bridging oxygen atoms, therefore this surface is        fairly hydrophobic. The unique shape and physical-chemical        property of the cavity enable the cyclodextrin molecules to        absorb (form inclusion complexes with) organic molecules or        parts of organic molecules which can fit into the cavity. Many        perfume molecules can fit into the cavity.    -   Cyclodextrin molecules are described in U.S. Pat. No. 5,714,137,        and U.S. Pat. No. 5,942,217. Suitable levels of cyclodextrin are        from about 0.1% to about 5%, alternatively from about 0.2% to        about 4%, alternatively from about 0.3% to about 3%,        alternatively from about 0.4% to about 2%, by weight of the        composition.    -   Buffering Agent—The composition can include a buffering agent        which may be alkaline, acidic or neutral. The buffer can be used        in the composition for maintaining the desired pH. The        composition may have a pH from about 3 to about 10, from about 4        to about 9, from about 5 to about 8, from about 6 to about 7, or        it may have a pH of about 6.5. One unique feature of the        polyvinyl amine malodor control polymers is its ability to        maintain active nitrogen sites at high pH levels which can help        enhance the antibacterial effect which comes, at least in part,        from the nitrogen sites. Suitable buffering agents include, for        example, hydrochloric acid, sodium hydroxide, potassium        hydroxide, and combinations thereof.    -   The compositions can contain at least about 0%, alternatively at        least about 0.001%, alternatively at least about 0.01%, by        weight of the composition, of a buffering agent. The composition        may also contain no more than about 1%, alternatively no more        than about 0.75%, alternatively no more than about 0.5%, by        weight of the composition, of a buffering agent.    -   Solubilizer—The composition can contain a solubilizer. A        suitable solubilizer can be, for example, a surfactant, such as        a no-foaming or low-foaming surfactant. Suitable surfactants are        nonionic surfactants, cationic surfactants, amphoteric        surfactants, zwitterionic surfactants, and mixtures thereof.    -   Suitable solubilizers include, for example, hydrogenated castor        oil, polyoxyethylene 2 stearyl ether, polyoxyethylene 20 stearyl        ether, and combinations thereof. One suitable hydrogenated        castor oil that may be used in the present composition is        polyoxyethylene hydrogenated castor oil.    -   When the solubilizing agent is present, it is typically present        at a level of from about 0.01% to about 5%, alternatively from        about 0.01% to about 3%, alternatively from about 0.05% to about        1%, alternatively from about 0.01% to about 0.05%, by weight of        the composition.    -   Preservatives—The composition can include a preservative. The        preservative is included in an amount sufficient to prevent        spoilage or prevent growth of inadvertently added microorganisms        for a specific period of time, but not sufficient enough to        contribute to the odor neutralizing performance of the        composition. In other words, the preservative is not being used        as the antimicrobial compound to kill microorganisms on the        surface onto which the composition is deposited in order to        eliminate odors produced by microorganisms. Instead, it is being        used to prevent spoilage of the composition in order to increase        shelf-life.    -   The preservative can be any organic preservative material which        will not cause damage to fabric appearance, e.g., discoloration,        coloration, bleaching. Suitable water-soluble preservatives        include organic sulfur compounds, halogenated compounds, cyclic        organic nitrogen compounds, low molecular weight aldehydes,        parabens, propane diol materials, isothiazolinones, quaternary        compounds, benzoates, low molecular weight alcohols,        dehydroacetic acid, phenyl and phenoxy compounds, or mixtures        thereof.    -   Non-limiting examples of commercially available water-soluble        preservatives include a mixture of about 77%        5-chloro-2-methyl-4-isothiazolin-3-one and about 23%        2-methyl-4-isothiazolin-3-one, a broad spectrum preservative        available as a 1.5% aqueous solution under the trade name        Kathon® CG by Rohm and Haas Co.; 5-bromo-5-nitro-1,3-dioxane,        available under the tradename Bronidox L® from Henkel;        2-bromo-2-nitropropane-1,3-diol, available under the trade name        Bronopol® from Inolex; 1,1′-hexamethylene        bis(5-(p-chlorophenyl)biguanide), commonly known as        chlorhexidine, and its salts, e.g., with acetic and digluconic        acids; a 95:5 mixture of        1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione and        3-butyl-2-iodopropynyl carbamate, available under the trade name        Glydant Plus® from Lonza;        N-[1,3-bis(hydroxymethyl)2,5-dioxo-4-imidazolidinyl]-N,N′-bis(hydroxy-methyl)        urea, commonly known as diazolidinyl urea, available under the        trade name Germall® II from Sutton Laboratories, Inc.;        N,N″-methylenebis{N′-[1-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]-urea},        commonly known as imidazolidinyl urea, available, e.g., under        the trade name Abiol® from 3V-Sigma, Unicide U-13® from        Induchem, Germall 115® from Sutton Laboratories, Inc.;        polymethoxy bicyclic oxazolidine, available under the trade name        Nuosept® C from Hüls America; formaldehyde; glutaraldehyde;        polyaminopropyl biguanide, available under the trade name        Cosmocil CQ® from ICI Americas, Inc., or under the trade name        Mikrokill® from Brooks, Inc; dehydroacetic acid; and        benzsiothiazolinone available under the trade name Koralone™        B-119 from Rohm and Hass Corporation.    -   Suitable levels of preservative can range from about 0.0001% to        about 0.5%, alternatively from about 0.0002% to about 0.2%,        alternatively from about 0.0003% to about 0.1%, by weight of the        composition.

B. Body Spray

A body spray can contain, for example, a carrier, perfume, a deodorantactive, odor entrappers, propellant, or combinations thereof. The bodyspray compositions can be applied as a liquid.

-   -   Carrier—A carrier suitable for use in a body spray can include,        water, alcohol, or combinations thereof. The carrier may be        present in an amount of about 1% to about 99.5%, about 25% to        about 99.5%, about 50% to about 99.5%, about 75% to about 99.5%        about 80% to about 99.5%, from about 15% to about 45%, or any        combination of the end points and points encompassed within the        ranges, by weight of the composition. A suitable example of an        alcohol can include ethanol.    -   Propellant—The compositions described herein can include a        propellant. Some examples of propellants include compressed air,        nitrogen, inert gases, carbon dioxide, and mixtures thereof.        Propellants may also include gaseous hydrocarbons like propane,        n-butane, isobutene, cyclopropane, and mixtures thereof.        Halogenated hydrocarbons like 1,1-difluoroethane may also be        used as propellants. Some non-limiting examples of propellants        include 1,1,1,2,2-pentafluoroethane, 1,1,1,2-tetrafluoroethane,        1,1,1,2,3,3,3-heptafluoropropane,        trans-1,3,3,3-tetrafluoroprop-1-ene, dimethyl ether,        dichlorodifluoromethane (propellant 12),        1,1-dichloro-1,1,2,2-tetrafluoroethane (propellant 114),        1-chloro-1,1-difluoro-2,2-trifluoroethane (propellant 115),        1-chloro-1,1-difluoroethylene (propellant 142B),        1,1-difluoroethane (propellant 152A), monochlorodifluoromethane,        and mixtures thereof. Some other propellants suitable for use        include, but are not limited to, A-46 (a mixture of isobutane,        butane and propane), A-31 (isobutane), A-17 (n-butane), A-108        (propane), AP70 (a mixture of propane, isobutane and n-butane),        AP40 (a mixture of propane, isobutene and n-butane), AP30 (a        mixture of propane, isobutane and n-butane), and 152A (1,1        difluoroethane). The propellant may have a concentration from        about 15%, 25%, 30%, 32%, 34%, 35%, 36%, 38%, 40%, or 42% to        about 70%, 65%, 60%, 54%, 52%, 50%, 48%, 46%, 44%, or 42%, or        any combination thereof, by weight of the total fill of        materials stored within the container.

C. Invisible Solid

Invisible solid antiperspirant compositions as described herein cancontain a primary structurant, an antiperspirant active, a perfume, andadditional chassis ingredient(s). The antiperspirant composition canfurther comprise other optional ingredient(s). The compositions can bein the form of a solid stick. The compositions can have a producthardness of about 600 gram force or more. The compositions may be freeof dipropylene glycol, added water, castor wax, or any combinationthereof. The antiperspirant composition may be anhydrous. Theantiperspirant composition may be free of added water.

-   -   Hardness—The invisible solid can have a product hardness of        least about 600 gram·force, more specifically from about 600        gram·force to about 5,000 gram·force, still more specifically        from about 750 gram force to about 2,000 gram·force, and yet        more specifically from about 800 gram·force to about 1,400        gram·force.    -   The term “product hardness” or “hardness” as used herein is a        reflection of how much force is required to move a penetration        cone a specified distance and at a controlled rate into an        antiperspirant composition under the test conditions described        herein below. Higher values represent harder product, and lower        values represent softer product. These values are measured at        27° C., 15% relative humidity, using a TA-XT2 Texture Analyzer,        available from Texture Technology Corp., Scarsdale, N.Y., U.S.A.        The product hardness value as used herein represents the peak        force required to move a standard 45-degree angle penetration        cone through the composition for a distance of 10 mm at a speed        of 2 mm/second. The standard cone is available from Texture        Technology Corp., as part number TA-15, and has a total cone        length of about 24.7 mm, angled cone length of about 18.3 mm,        and a maximum diameter of the angled surface of the cone of        about 15.5 mm. The cone is a smooth, stainless steel        construction and weighs about 17.8 grams.    -   Primary Structurants—The invisible solid can comprise a suitable        concentration of a primary structurant to help provide the        antiperspirant with the desired viscosity, rheology, texture        and/or product hardness, or to otherwise help suspend any        dispersed solids or liquids within the composition.    -   The term “solid structurant” as used herein means any material        known or otherwise effective in providing suspending, gelling,        viscosifying, solidifying, and/or thickening properties to the        composition or which otherwise provide structure to the final        product form. These solid structurants include gelling agents,        and polymeric or non-polymeric or inorganic thickening or        viscosifying agents. Such materials will typically be solids        under ambient conditions and include organic solids, crystalline        or other gellants, inorganic particulates such as clays or        silicas, or combinations thereof.    -   The concentration and type of solid structurant selected for use        in the antiperspirant compositions will vary depending upon the        desired product hardness, rheology, and/or other related product        characteristics. For most structurants suitable for use herein,        the total structurant concentration ranges from about 5% to        about 35%, more typically from about 10% to about 30%, or from        about 7% to about 20%, by weight of the composition.    -   Non-limiting examples of suitable primary structurants include        stearyl alcohol and other fatty alcohols; hydrogenated castor        wax (e.g., Castorwax MP80, Castor Wax, etc.); hydrocarbon waxes        include paraffin wax, beeswax, carnauba, candelilla, spermaceti        wax, ozokerite, ceresin, baysberry, synthetic waxes such as        Fischer-Tropsch waxes, and microcrystalline wax; polyethylenes        with molecular weight of 200 to 1000 daltons; solid        triglycerides; behenyl alcohol, or combinations thereof.    -   Other non-limiting examples of primary structurants suitable for        use herein are described in U.S. Pat. No. 5,976,514 and U.S.        Pat. No. 5,891,424, the descriptions of which are incorporated        herein by reference.    -   Antiperspirant Active—The antiperspirant stick compositions can        comprise a particulate antiperspirant active suitable for        application to human skin. The concentration of antiperspirant        active in the composition should be sufficient to provide the        desired perspiration wetness and odor control from the        antiperspirant stick formulation selected.    -   The antiperspirant stick compositions can comprise an        antiperspirant active at concentrations of from about 0.5% to        about 60%, and more specifically from about 5% to about 35%, by        weight of the composition. These weight percentages are        calculated on an anhydrous metal salt basis exclusive of water        and any complexing agents such as, for example, glycine, and        glycine salts. The antiperspirant active as formulated in the        composition can be in the form of dispersed particulate solids        having an average particle size or equivalent diameter of less        than about 100 microns, more specifically less than about 20        microns, and even more specifically less than about 10 microns.    -   The antiperspirant active for use in the anhydrous        antiperspirant compositions of the present invention can include        any compound, composition or other material having        antiperspirant activity. More specifically, the antiperspirant        actives may include astringent metallic salts, especially        inorganic and organic salts of aluminum, zirconium and zinc, as        well as mixtures thereof. Even more specifically, the        antiperspirant actives may include aluminum-containing and/or        zirconium-containing salts or materials, such as, for example,        aluminum halides, aluminum chlorohydrate, aluminum        hydroxyhalides, zirconyl oxyhalides, zirconyl hydroxyhalides,        and mixtures thereof.    -   Aluminum salts for use in the anhydrous antiperspirant stick        compositions include those that conform to the formula:

Al₂(OH)_(a)Cl_(b) .xH₂O,

-   -    wherein a is from about 2 to about 5; the sum of a and b is        about 6; x is from about 1 to about 6; and a, b, and x may have        non-integer values. More specifically, aluminum chlorohydroxides        referred to as “5/6 basic chlorohydroxide” can be used, wherein        a=5, and “2/3 basic chlorohydroxide”, wherein a=4. Processes for        preparing aluminum salts are disclosed in U.S. Pat. No.        3,887,692; U.S. Pat. No. 3,904,741; U.S. Pat. No. 4,359,456; and        British Patent Specification 2,048,229, the disclosures of which        are incorporated herein by reference for the purpose of        describing processes for preparing aluminum salts. Mixtures of        aluminum salts are described in British Patent Specification        1,347,950, which description is also incorporated herein by        reference.    -   Zirconium salts for use in the anhydrous antiperspirant stick        compositions include those which conform to the formula:

ZrO(OH)_(2-a)Cl_(a) .xH₂O,

-   -    wherein a is from about 1.5 to about 1.87; x is from about 1 to        about 7; and a and x may both have non-integer values. These        zirconium salts are described in Belgian Patent 825,146,        Schmitz, issued Aug. 4, 1975, which description is incorporated        herein by reference. Zirconium salts that additionally contain        aluminum and glycine, commonly known as “ZAG complexes,” are        believed to be especially beneficial. These ZAG complexes        contain aluminum chlorohydroxide and zirconyl hydroxy chloride        conforming to the above-described formulas. Such ZAG complexes        are described in U.S. Pat. No. 3,792,068; Great Britain Patent        Application 2,144,992; and U.S. Pat. No. 4,120,948, disclosures        of which are incorporated herein by reference for the limited        purpose of describing ZAG complexes.

Also suitable for use herein are enhanced efficacy aluminum-zirconiumchlorohydrex-amino acid which typically has the empirical formula:

Al_(n)Zr(OH)_([3n+4-m(n+1)])(Cl)_([m(n+1)])-AA_(q)

-   -    where n is 2.0 to 10.0, preferably 3.0 to 8.0; m is about 0.48        to about 1.11 (which corresponds to M:Cl approximately equal to        2.1-0.9), preferably about 0.56 to about 0.83 (which corresponds        to M:Cl approximately equal to 1.8-1.2); q is about 0.8 to about        4.0, preferably about 1.0 to 2.0; and AA is an amino acid such        as glycine, alanine, valine, serine, leucine, isoleucine,        β-alanine, cysteine, β-amino-n-butyric acid, or        γ-amino-n-butyric acid, preferably glycine. These salts also        generally have some water of hydration associated with them,        typically on the order of 1 to 5 moles per mole of salt        (typically, about 1% to about 16%, more typically about 4% to        about 13% by weight). These salts are generally referred to as        aluminum-zirconium trichlorohydrex or tetrachlorohydrex when the        Al:Zr ratio is between 2 and 6 and as aluminum-zirconium        pentachlorohydrex or octachlorohydrex when the Al:Zr ratio is        between 6 and 10. The term “aluminum-zirconium chlorohydrex” is        intended to embrace all of these forms. The preferred        aluminum-zirconium salt is aluminum-zirconium        chlorohydrex-glycine. Additional examples of suitable high        efficacy antiperspirant actives can include Aluminum Zirconium        Pentachlorohydrex Glycine, Aluminum Zirconium Octachlorohydrex        Glycine, or a combination thereof. These high efficacy actives        are more fully described in U.S. App. Pub. No. 2007/0003499 by        Shen et al. filed Jun. 30, 2005.

Additional Chassis Ingredients

-   -   Additional Structurant—The antiperspirant composition can        further comprise an additional structurant. The additional        structurant may be present in an amount from 1% to about 10%, by        weight of the composition. The additional structurant(s) will        likely be present at an amount less than the primary        structurant. Non-limiting examples of suitable additional        structurants include stearyl alcohol and other fatty alcohols;        hydrogenated castor wax (e.g., Castorwax MP80, Castor Wax,        etc.); hydrocarbon waxes include paraffin wax, beeswax,        carnauba, candelilla, spermaceti wax, ozokerite, ceresin,        baysberry, synthetic waxes such as Fisher-Tropsch waxes, and        microcrystalline wax; polyethylenes with molecular weight of 200        to 1000 daltons; and solid triglycerides; behenyl alcohol, or        combinations thereof. Other non-limiting examples of additional        structurants suitable for use herein are described in U.S. Pat.        No. 5,976,514 and U.S. Pat. No. 5,891,424.    -   Solvent—The antiperspirant composition can comprise a solvent at        concentrations ranging from about 20% to about 80%, and more        specifically from about 30% to about 70%, by weight of the        composition. The solvent can be a volatile silicone which may be        cyclic or linear.    -   “Volatile silicone” as used herein refers to those silicone        materials that have measurable vapor pressure under ambient        conditions. Non-limiting examples of suitable volatile silicones        are described in Todd et al., “Volatile Silicone Fluids for        Cosmetics”, Cosmetics and Toiletries, 91:27-32 (1976), which        descriptions are incorporated herein by reference. The volatile        silicone can be a cyclic silicone having from 3 to 7, and more        specifically from 5 to 6, silicon atoms, and still more        specifically 5, like cyclopentasiloxane. These cyclic silicone        materials will generally have viscosities of less than about 10        centistokes at 25° C. The volatile silicone can also be linear,        suitable volatile linear silicone materials for use in the        antiperspirant compositions include those represented by the        formula:

-   -    wherein n is from 1 to 7, and more specifically from 2 to 3.        These linear silicone materials will generally have viscosities        of less than about 5 centistokes at 25° C. Specific examples of        volatile silicone solvents suitable for use in the        antiperspirant compositions include, but are not limited to,        Cyclomethicone D-5; GE 7207 and GE 7158 (commercially available        from General Electric Co.); Dow Corning 344; Dow Corning 345;        Dow Corning 200; and DC1184 (commercially available from Dow        Corning Corp.); and SWS-03314 (commercially available from SWS        Silicones).    -   Non-Volatile Organic Fluids—Non-volatile organic fluids may be        present, for example, in an amount of about 15% or less, by        weight of the composition. Non-limiting examples of nonvolatile        organic fluids include mineral oil, PPG-14 butyl ether,        isopropyl myristate, petrolatum, butyl stearate, cetyl        octanoate, butyl myristate, myristyl myristate, C12-15        alkylbenzoate (e.g., Finsolv™), octyldodecanol, isostearyl        isostearate, octododecyl benzoate, isostearyl lactate,        isostearyl palmitate, and isobutyl stearate.    -   Adjunct Ingredients—The anhydrous antiperspirant compositions        can further comprise any optional material that is known for use        in antiperspirant and deodorant compositions or other personal        care products, or which is otherwise suitable for topical        application to human skin. One example of optional materials are        clay mineral powders such as talc, mica, sericite, silica,        magnesium silicate, synthetic fluorphlogopite, calcium silicate,        aluminum silicate, bentonite and montomorillonite; pearl        pigments such as alumina, barium sulfate, calcium secondary        phosphate, calcium carbonate, titanium oxide, finely divided        titanium oxide, zirconium oxide, zinc oxide, hydroxy apatite,        iron oxide, iron titrate, ultramarine blue, Prussian blue,        chromium oxide, chromium hydroxide, cobalt oxide, cobalt        titanate, titanium oxide coated mica; organic powders such as        polyester, polyethylene, polystyrene, methyl methacrylate resin,        cellulose, 12-nylon, 6-nylon, styrene-acrylic acid copolymers,        poly propylene, vinyl chloride polymer, tetrafluoroethylene        polymer, boron nitride, fish scale guanine, laked tar color        dyes, laked natural color dyes; and combinations thereof. Talc,        if used at higher levels can produce a significant amount of        white residue which has been found to be a consumer negative for        product acceptance. Therefore it is best to limit the        composition to less than 10%, less than about 8%, less than        about 6%, or less than about 3%, by weight of the composition.        Nonlimiting examples of other optional materials include        emulsifiers, distributing agents, antimicrobials, pharmaceutical        or other topical active, preservatives, surfactants, and so        forth. Examples of such optional materials are described in U.S.        Pat. No. 4,049,792; U.S. Pat. No. 5,019,375; and U.S. Pat. No.        5,429,816; which descriptions are incorporated herein by        reference.

D. Soft Solid

Soft solid composition can comprise volatile silicone, antiperspirantactive, gellant, residue masking material, or combinations thereof. Inaddition, soft solids generally have a hardness value after dispensingof about 500 gram force or less.

-   -   Volatile Silicone Solvent—The soft solid can comprises a        volatile silicone solvent at concentrations ranging from about        20% to about 80%, preferably from about 30% to about 70%, more        preferably from about 45% to about 70%, by weight of the        composition. The volatile silicone of the solvent may be cyclic        or linear.    -   “Volatile silicone” as used herein refers to those silicone        materials which have measurable vapor pressure under ambient        conditions. Nonlimiting examples of suitable volatile silicones        are described in Todd et al., “Volatile Silicone Fluids for        Cosmetics”, Cosmetics and Toiletries, 91:27-32 (1976), which        descriptions are incorporated herein by reference. Preferred        volatile silicone materials are those having from about 3 to        about 7, preferably from about 4 to about 5, silicon atoms.        Cyclic volatile silicones are preferred for use in the        antiperspirant compositions herein, and include those        represented by the formula:

-   -    wherein n is from about 3 to about 7, preferably from about 4        to about 5, most preferably 5. These cyclic silicone materials        will generally have viscosities of less than about 10        centistokes at 25° C. Linear volatile silicone materials        suitable for use in the antiperspirant compositions include        those represented by the formula:

-   -    wherein n is from about 1 to about 7, preferably from about 2        to about 3. These linear silicone materials will generally have        viscosities of less than about 5 centistokes at 25° C. Specific        examples of volatile silicone solvents suitable for use in the        antiperspirant compositions include, but are not limited to,        Cyclomethicone 0-5 (commercially available from G. E.        Silicones), Dow Corning 344, Dow Corning 345 and Dow Corning 200        (commercially available from Dow Corning Corp.), GE 7207 and        7158 (commercially available from General Electric Co.) and        SWS-03314 (commercially available from SWS Silicones Corp.).    -   Gellant Material—The soft solid can include a gellant material        comprising fatty alcohols having from about 20 to about 60        carbon atoms, or combinations thereof, at concentrations ranging        from about 0.1% to about 8% by weight of the composition. The        gellant material, when combined with the volatile silicone        solvent described hereinbefore, provides the composition with a        physically stable structure within which the particulate        antiperspirant materials are dispersed, and maintained as such        over an extended period of time. Specifically, the gellant        material can comprise saturated or unsaturated, substituted or        unsubstituted, fatty alcohols or mixtures of fatty alcohols        having from about 20 to about 60 carbons atoms, preferably from        about 20 to about 40 carbon atoms. Preferred are combinations of        the fatty alcohols. The fatty alcohol gellants are preferably        saturated, unsubstituted monohydric alcohols or combinations        thereof, which have a melting point of at less than about 110°        C., more preferably from about 60° to about 110° C., even more        preferably between about 100° C. and 110° C.    -   It has been found that this fatty alcohol-based gellant        material, when combined with volatile silicone solvents provides        a stable structure for maintaining a dispersion of particulate        antiperspirant material in a topical formulation without the        necessity of using conventional particulate thickening agents.        This gellant material is especially useful in maintaining the        physical stability of particulate dispersions containing higher        concentrations of volatile silicone solvents.    -   It was also found that penetration force values for the        antiperspirant compositions can be controlled by adjusting total        fatty alcohol concentrations. In controlling penetration force        values in this manner, there is no longer a need to use organic        solvents or thickening agents to control penetration force        values, which solvents or thickening agents often add cost to        the formulation, introduce additional compatibility issues, and        often contribute undesirable cosmetics such as prolonged        stickiness, difficulty in ease of spreading, increased dry-down        times and reduced dry feel after application.    -   Specific concentrations of the gellant materials can be selected        according to the desired penetration force value. For roll-on        formulations having a penetration force value of from about 20        gram·force to about 100 gram·force, gellant material        concentrations preferably range from about 0.1% to about 3%,        preferably from about 1.5% to about 3%, by weight of the        antiperspirant composition. For other cream formulations,        including those formulations suitable for use in cream        applicator devices, which have a penetration force value of from        about 100 gram·force to about 500 gram·force, gellant material        concentrations preferably range from about 3% to about 8%,        preferably from about 3% to about 6%, by weight of the        antiperspirant composition.    -   Specific examples of fatty alcohol gellants for use in the        antiperspirant compositions that are commercially available        include, but are not limited to, Unilin® 425, Unilin® 350,        Unilin®550 and Unilin® 700 (supplied by Petrolite)    -   Residue Masking Material—The soft solid compositions can further        comprise a nonvolatile emollient as a residue masking material.        Such materials and their use in antiperspirant products are well        known in the antiperspirant art, and any such material may be        incorporated into the composition of the present invention,        provided that such optional material is compatible with the        essential elements of the composition, or does not unduly impair        product performance or cosmetics. Concentrations of the optional        residue masking material can range from about 0.1% to about 40%,        preferably from about 1% to about 10%, by weight of the        antiperspirant composition. These optional materials can be        liquid at ambient temperatures, and can be nonvolatile. The term        “nonvolatile” as used in this context refers to materials which        have a boiling point under atmospheric pressure of at least        about 200° C. Nonlimiting examples of suitable residue masking        materials for use in the antiperspirant products include butyl        stearate, diisopropyl adipate, petrolatum, nonvolatile        silicones, octyldodecanol, phenyl trimethicone, isopropyl        myristate, C12-15 ethanol benzoates and PPG-14 Butyl Ether.        Residue masking materials are described, for example, in U.S.        Pat. No. 4,985,238, which description is incorporated herein by        reference.    -   Other Materials—The soft solid compositions can further comprise        one, or more, other materials which modify the physical        characteristics of the compositions or serve as additional        “active” components when deposited on the skin. Many such        materials are known in the antiperspirant art and can be used in        the antiperspirant compositions herein, provided that such        optional materials are compatible with the essential materials        described herein, or do not otherwise unduly impair product        performance. Non limiting examples of materials can include        active components such as bacteriostats and fungiostats, and        “non-active” components such as colorants, perfumes, cosmetic        powders, emulsifiers, chelants, distributing agents,        preservatives, and wash-off aids. Examples of such optional        materials are described in U.S. Pat. No. 4,049,792; Canadian        Patent 1,164,347; U.S. Pat. No. 5,019,375; and U.S. Pat. No.        5,429,816; which descriptions are incorporated herein by        reference.

E. Aerosol

An aerosol composition can comprise a concentrate, a propellant, or acombination thereof. Alcohol is a predominant component of theconcentrates provided herein. Useful alcohols include C₁-C₃ alcohols,with the preferred alcohol being ethanol. In certain examples, thealcohol is employed at a concentration level of from at least about 40%,50% or 55% to about 80%, by weight of the concentrate.

An antiperspirant active is dissolved in the alcohol, at a level of fromabout 1% to about 15%, by weight of the concentrate. Variousantiperspirant actives can be employed, including, for example, aluminumchloride, aluminum chlorohydrate, aluminum chlorohydrex, aluminumchlorohydrex PG, aluminum chlorohydrex PEG, aluminum dichlorohydrate,aluminum dichlorohydrex PG, aluminum dichlorohydrex PEG, aluminumsesquichlorohydrate, aluminum sesquichlorohydrex PG, aluminumsesquichlorohydrex PEG, aluminum sulfate, aluminum zirconiumoctachlorohydrate, aluminum zirconium octachlorohydrex GLY, aluminumzirconium pentachlorohydrate, aluminum zirconium pentachlorohydrex GLY,aluminum zirconium tetrachlorohydrate, aluminum zirconiumtrichlorohydrate, aluminum zirconium tetrachlorohydrate GLY, andaluminum zirconium trichlorohydrate GLY. In one example, aluminumchlorohydrex PG is the chosen antiperspirant active.

The antiperspirant concentrates can also include an oil or a mixture oftwo or more oils. Useful oils include, for example, volatile siliconeoils and non-volatile organic oils. “Volatile silicone”, as used herein,refers to those silicone materials that have measurable vapor pressureunder ambient conditions. Non-limiting examples of suitable volatilesilicones are described in Todd et al., “Volatile Silicone Fluids forCosmetics”, Cosmetics and Toiletries, 91:27-32 (1976). The volatilesilicone can be a cyclic silicone having from at least about 3 siliconeatoms or from at least about 5 silicone atoms but no more than about 7silicone atoms or no more than about 6 silicone atoms. For example,volatile silicones can be used which conform to the formula:

wherein n is from about 3 or from about 5 but no more than about 7 or nomore than about 6. These volatile cyclic silicones generally have aviscosity of less than about 10 centistokes at 25° C. Suitable volatilesilicones for use herein include, but are not limited to, CyclomethiconeD5 (commercially available from G. E. Silicones); Dow Corning 344, andDow Corning 345 (commercially available from Dow Corning Corp.); and GE7207, GE 7158 and Silicone Fluids SF-1202 and SF-1173 (available fromGeneral Electric Co.). SWS-03314, SWS-03400, F-222, F-223, F-250, F-251(available from SWS Silicones Corp.); Volatile Silicones 7158, 7207,7349 (available from Union Carbide); MASIL SF-V (available from Mazer)and combinations thereof. Suitable volatile silicone oils can alsoinclude linear silicone oils such as, for example, DC200 (1 cSt), DC200(0.65 cSt), and DC2-1184, all of which are available from Dow CorningCorp. In certain examples, the volatile silicone oil can have aviscosity of less than 10 centistokes at 25° C.

Non-volatile organic, emollient oils can also be employed. Arepresentative, non-limiting list of emollient oils includes CETIOL CC(dicaprylyl carbonate), CETIOL OE (dicaprylyl ether), CETIOL S(diethylhexylcyclohexane), and CETIOL B (dibutyl adipate), all of whichare available from Cognis, and LEXFEEL 7 (neopentyl glycol diheptanoate)from Inolex. In certain examples, the organic emollient oils have aviscosity of less than 50 centistokes at 25° C. The term “organicemollient oil” as used herein means silicon-free emollient oils that areliquid at 25° C., and that are safe and light to skin and can bemiscible with volatile silicone oils (as described above) and theantiperspirant active-alcohol solution in the concentration rangesdescribed below. The oil or mixture of oils is generally included in theconcentrate formulas at a level of from about 5% to about 45%, by weightof the concentrate. This viscosity ranges noted above in connection withthe different classes of oil can facilitate desired spray rates andpatterns, and can help minimize nozzle clogging. To provide desired skinfeel, minimal nozzle clogging, and good concentrate stability, the ratioof alcohol to volatile silicone oil is preferably greater than 1.0,1.35, or 1.5. And in examples having both a volatile silicone oil and anorganic emollient oil, the ratio of alcohol to total oil is preferablygreater than or equal to about 0.90. The oils in certain examples aremiscible with the alcohol and antiperspirant active solution. Althoughvarious levels of miscibility are acceptable, the oils are preferablymiscible enough with the alcohol and antiperspirant active solution toyield a concentrate having a clear appearance.

The antiperspirant compositions can also include residue-masking agentsand propellants as discussed above.

Additional Consumer Product Ingredients/Adjunct Materials

While not essential for the purposes of the present invention, thenon-limiting list of consumer product ingredients/adjuncts illustratedhereinafter are suitable for use in the instant compositions and may bedesirably incorporated in certain aspects of the invention, for exampleto assist or enhance cleaning performance, for treatment of thesubstrate to be cleaned, or to modify the aesthetics of the compositionas is the case with perfumes, colorants, dyes or the like. The precisenature of these additional components, and levels of incorporationthereof, will depend on the physical form of the composition and thenature of the fabric treatment operation for which it is to be used.Suitable adjunct materials include, but are not limited to, surfactants,builders, chelating agents, dye transfer inhibiting agents, dispersants,enzymes, and enzyme stabilizers, catalytic materials, bleach activators,hydrogen peroxide, sources of hydrogen peroxide, preformed peracids,polymeric dispersing agents, clay soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, hueing dyes, perfumes, perfumedelivery systems, structure elasticizing agents, carriers, structurants,hydrotropes, processing aids, solvents, pigments and/or fabric softeneractives and clothes softening agents compatible with detergents,anti-bacterials, anti-microbials, and anti-fungals.

As stated, the adjunct ingredients are not essential to Applicants'compositions. Thus, certain aspects of Applicants' compositions do notcontain one or more of the following adjuncts materials: surfactants,builders, chelating agents, dye transfer inhibiting agents, dispersants,enzymes, and enzyme stabilizers, catalytic materials, bleach activators,hydrogen peroxide, sources of hydrogen peroxide, preformed peracids,polymeric dispersing agents, clay soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, hueing dyes, perfumes, perfumedelivery systems structure elasticizing agents, carriers, hydrotropes,processing aids, solvents, pigments and/or fabric softener actives,anti-bacterial/microbial. However, when one or more adjuncts arepresent, such one or more adjuncts may be present as detailed below.

Rheology Modifier—

The liquid compositions of the present invention may comprise a rheologymodifier. The rheology modifier may be selected from the groupconsisting of non-polymeric crystalline, hydroxy-functional materials,polymeric rheology modifiers which impart shear thinning characteristicsto the aqueous liquid matrix of the composition. In one aspect, suchrheology modifiers impart to the aqueous liquid composition a high shearviscosity, at 20 sec⁻¹ shear rate and at 21° C., of from 1 to 7000 cpsand a viscosity at low shear (0.5 sec⁻¹ shear rate at 21° C.) of greaterthan 1000 cps, or even 1000 cps to 200,000 cps. In one aspect, forcleaning and treatment compositions, such rheology modifiers impart tothe aqueous liquid composition a high shear viscosity, at 20 sec⁻¹ andat 21° C., of from 50 to 3000 cps and a viscosity at low shear (0.5sec⁻¹ shear rate at 21° C.) of greater than 1000 cps, or even 1000 cpsto 200,000 cps. Viscosity according to the present invention is measuredusing an AR 2000 rheometer from TA instruments using a plate steelspindle having a plate diameter of 40 mm and a gap size of 500 μm. Thehigh shear viscosity at 20 sec⁻¹ and low shear viscosity at 0.5 sec⁻¹can be obtained from a logarithmic shear rate sweep from 0.1 sec⁻¹ to 25sec⁻¹ in 3 minutes time at 21° C. Crystalline hydroxyl functionalmaterials are rheology modifiers which form thread-like structuringsystems throughout the matrix of the composition upon in situcrystallization in the matrix. Polymeric rheology modifiers arepreferably selected from polyacrylates, polymeric gums, other non-gumpolysaccharides, and combinations of these polymeric materials.Generally the rheology modifier will comprise from 0.01% to 1% byweight, preferably from 0.05% to 0.75% by weight, more preferably from0.1% to 0.5% by weight, of the compositions herein.

Structuring agents which are especially useful in the compositions ofthe present invention may comprise non-polymeric (except forconventional alkoxylation), crystalline hydroxy-functional materialswhich can form thread-like structuring systems throughout the liquidmatrix when they are crystallized within the matrix in situ. Suchmaterials can be generally characterized as crystalline,hydroxyl-containing fatty acids, fatty esters or fatty waxes. In oneaspect, rheology modifiers include crystalline, hydroxyl-containingrheology modifiers include castor oil and its derivatives. In oneaspect, rheology modifiers include hydrogenated castor oil derivativessuch as hydrogenated castor oil and hydrogenated castor wax.Commercially available, castor oil-based, crystalline,hydroxyl-containing rheology modifiers include THIXCIN™ from Rheox, Inc.(now Elementis).

Other types of rheology modifiers, besides the non-polymeric,crystalline, hydroxyl-containing rheology modifiers describedheretofore, may be utilized in the liquid detergent compositions herein.Polymeric materials which provide shear-thinning characteristics to theaqueous liquid matrix may also be employed. Suitable polymeric rheologymodifiers include those of the polyacrylate, polysaccharide orpolysaccharide derivative type. Polysaccharide derivatives typicallyused as rheology modifiers comprise polymeric gum materials. Such gumsinclude pectine, alginate, arabinogalactan (gum Arabic), carrageenan,gellan gum, xanthan gum and guar gum. If polymeric rheology modifiersare employed herein, a preferred material of this type is gellan gum.Gellan gum is a heteropolysaccharide prepared by fermentation ofPseudomonaselodea ATCC 31461. Gellan gum is commercially marketed by CPKelco U.S., Inc. under the KELCOGEL tradename.

A further alternative and suitable rheology modifier include acombination of a solvent and a polycarboxylate polymer. Morespecifically the solvent may be an alkylene glycol. In one aspect, thesolvent may comprise dipropylene glycol. In one aspect, thepolycarboxylate polymer may comprise a polyacrylate, polymethacrylate ormixtures thereof. In one aspect, solvent may be present, based on totalcomposition weight, at a level of from 0.5% to 15%, or from 2% to 9% ofthe composition. In one aspect, polycarboxylate polymer may be present,based on total composition weight, at a level of from 0.1% to 10%, orfrom 2% to 5%. In one aspect, the solvent component may comprise mixtureof dipropylene glycol and 1,2-propanediol. In one aspect, the ratio ofdipropylene glycol to 1,2-propanediol may be 3:1 to 1:3, or even 1:1. Inone aspect, the polyacrylate may comprise a copolymer of unsaturatedmono- or di-carbonic acid and C₁-C₃₀ alkyl ester of the (meth) acrylicacid. In another aspect, the rheology modifier may comprise apolyacrylate of unsaturated mono- or di-carbonic acid and C₁-C₃₀ alkylester of the (meth) acrylic acid. Such copolymers are available fromNoveon Inc under the tradename Carbopol Aqua 30®.

In the absence of rheology modifier and in order to impart the desiredshear thinning characteristics to the liquid composition, the liquidcomposition can be internally structured through surfactant phasechemistry or gel phases.

Hueing Dye—

The liquid laundry detergent composition may comprise a hueing dye. Thehueing dyes employed in the present laundry care compositions maycomprise polymeric or non-polymeric dyes, organic or inorganic pigments,or mixtures thereof. Preferably the hueing dye comprises a polymericdye, comprising a chromophore constituent and a polymeric constituent.The chromophore constituent is characterized in that it absorbs light inthe wavelength range of blue, red, violet, purple, or combinationsthereof upon exposure to light. In one aspect, the chromophoreconstituent exhibits an absorbance spectrum maximum from about 520nanometers to about 640 nanometers in water and/or methanol, and inanother aspect, from about 560 nanometers to about 610 nanometers inwater and/or methanol.

Although any suitable chromophore may be used, the dye chromophore ispreferably selected from benzodifuranes, methine, triphenylmethanes,napthalimides, pyrazole, naptho-quinone, anthraquinone, azo, oxazine,azine, xanthene, triphenodioxazine and phthalocyanine dye chromophores.Mono and di-azo dye chromophores are may be preferred.

The hueing dye may comprise a dye polymer comprising a chromophorecovalently bound to one or more of at least three consecutive repeatunits. It should be understood that the repeat units themselves do notneed to comprise a chromophore. The dye polymer may comprise at least 5,or at least 10, or even at least 20 consecutive repeat units. The repeatunit can be derived from an organic ester such as phenyl dicarboxylatein combination with an oxyalkyleneoxy and a polyoxyalkyleneoxy. Repeatunits can be derived from alkenes, epoxides, aziridine, carbohydrateincluding the units that comprise modified celluloses such ashydroxyalkylcellulose; hydroxypropyl cellulose; hydroxypropylmethylcellulose; hydroxybutyl cellulose; and, hydroxybutylmethylcellulose or mixtures thereof. The repeat units may be derivedfrom alkenes, or epoxides or mixtures thereof. The repeat units may beC₂-C₄ alkyleneoxy groups, sometimes called alkoxy groups, preferablyderived from C₂-C₄ alkylene oxide. The repeat units may be C₂-C₄ alkoxygroups, preferably ethoxy groups. For the purposes of the presentinvention, the at least three consecutive repeat units form a polymericconstituent. The polymeric constituent may be covalently bound to thechromophore group, directly or indirectly via a linking group. Examplesof suitable polymeric constituents include polyoxyalkylene chains havingmultiple repeating units. In one aspect, the polymeric constituentsinclude polyoxyalkylene chains having from 2 to about 30 repeatingunits, from 2 to about 20 repeating units, from 2 to about 10 repeatingunits or even from about 3 or 4 to about 6 repeating units. Non-limitingexamples of polyoxyalkylene chains include ethylene oxide, propyleneoxide, glycidol oxide, butylene oxide and mixtures thereof.

Surfactants—

The compositions according to the present invention may comprise asurfactant or surfactant system wherein the surfactant can be selectedfrom nonionic surfactants, anionic surfactants, cationic surfactants,ampholytic surfactants, zwitterionic surfactants, semi-polar nonionicsurfactants and mixtures thereof. The surfactant is typically present ata level of from about 0.1% to about 60%, from about 1% to about 50% oreven from about 5% to about 40% by weight of the subject composition.

Chelating Agents—

The compositions herein may contain a chelating agent. Suitablechelating agents include copper, iron and/or manganese chelating agentsand mixtures thereof. When a chelating agent is used, the compositionmay comprise from about 0.1% to about 15% or even from about 3.0% toabout 10% chelating agent by weight of the subject composition.

Dye Transfer Inhibiting Agents—

The compositions of the present invention may also include one or moredye transfer inhibiting agents. Suitable polymeric dye transferinhibiting agents include, but are not limited to, polyvinylpyrrolidonepolymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidoneand N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles ormixtures thereof. When present in a subject composition, the dyetransfer inhibiting agents may be present at levels from about 0.0001%to about 10%, from about 0.01% to about 5% or even from about 0.1% toabout 3% by weight of the composition.

Dispersants—

The compositions of the present invention can also contain dispersants.Suitable water-soluble organic materials include the homo- orco-polymeric acids or their salts, in which the polycarboxylic acidcomprises at least two carboxyl radicals separated from each other bynot more than two carbon atoms.

Perfumes—

The consumer product may comprise, either in neat form or via a deliverysystem, a perfume raw materials selected from the group consisting ofperfumes such as 3-(4-t-butylphenyl)-2-methyl propanal,3-(4-t-butylphenyl)-propanal, 3-(4-isopropylphenyl)-2-methylpropanal,3-(3,4-methylenedioxyphenyl)-2-methylpropanal, and2,6-dimethyl-5-heptenal, α-damascone, β-damascone, γ-damascone,Δ-damascenone, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone,methyl-7,3-dihydro-2H-1,5-benzodioxepine-3-one,2-[2-(4-methyl-3-cyclohexenyl-1-yl)propyl]cyclopentan-2-one,2-sec-butylcyclohexanone, and β-dihydro ionone, linalool, ethyllinalool,tetrahydrolinalool, and dihydromyrcenol.

Additional Perfume Delivery Technologies—

The compositions of the present invention may comprise one or moreperfume delivery technologies that stabilize and enhance the depositionand release of perfume ingredients from treated substrate. Such perfumedelivery technologies can also be used to increase the longevity ofperfume release from the treated substrate. Perfume deliverytechnologies, methods of making certain perfume delivery technologiesand the uses of such perfume delivery technologies are disclosed in US2007/0275866 A1.

In one aspect, the compositions of the present invention may comprisefrom about 0.001% to about 20%, preferably from about 0.01% to about10%, more preferably from about 0.05% to about 5%, most preferably fromabout 0.1% to about 0.5% by weight of the perfume delivery technology.In one aspect, said perfume delivery technologies may be selected fromthe group consisting of: pro-perfumes, polymer particles, functionalizedsilicones, polymer assisted delivery, molecule assisted delivery, fiberassisted delivery, amine assisted delivery, cyclodextrins, starchencapsulated accord, zeolite and inorganic carrier, additional perfumemicrocapsules, and mixtures thereof:

In one aspect, said perfume delivery technology may comprise anadditional encapsulated perfume such as additional perfume microcapsulesformed by at least partially surrounding a benefit agent with a wallmaterial. Said benefit agent may include materials selected from thegroup consisting of perfumes such as 3-(4-t-butylphenyl)-2-methylpropanal, 3-(4-t-butylphenyl)-propanal,3-(4-isopropylphenyl)-2-methylpropanal,3-(3,4-methylenedioxyphenyl)-2-methylpropanal, and2,6-dimethyl-5-heptenal, α-damascone, β-damascone, Δ-damascone,γ-damascenone, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone,methyl-7,3-dihydro-2H-1,5-benzodioxepine-3-one,2-[2-(4-methyl-3-cyclohexenyl-1-yl)propyl]cyclopentan-2-one,2-sec-butylcyclohexanone, and β-dihydro ionone, linalool, ethyllinalool,tetrahydrolinalool, and dihydromyrcenol. Suitable perfume materials canbe obtained from Givaudan Corp. of Mount Olive, N.J., USA, InternationalFlavors & Fragrances Corp. of South Brunswick, N.J., USA, or Quest Corp.of Naarden, Netherlands. In one aspect, the microcapsule wall materialmay comprise: melamine, polyacrylamide, silicones, silica, polystyrene,polyurea, polyurethanes, polyacrylate based materials, gelatin, styrenemalic anhydride, polyamides, and mixtures thereof. In one aspect, saidmelamine wall material may comprise melamine crosslinked withformaldehyde, melamine-dimethoxyethanol crosslinked with formaldehyde,and mixtures thereof. In one aspect, said polystyrene wall material maycomprise polyestyrene cross-linked with divinylbenzene. In one aspect,said polyurea wall material may comprise urea crosslinked withformaldehyde, urea crosslinked with gluteraldehyde, and mixturesthereof. In one aspect, said polyacrylate based materials may comprisepolyacrylate formed from methylmethacrylate/dimethylaminomethylmethacrylate, polyacrylate formed from amine acrylate and/ormethacrylate and strong acid, polyacrylate formed from carboxylic acidacrylate and/or methacrylate monomer and strong base, polyacrylateformed from an amine acrylate and/or methacrylate monomer and acarboxylic acid acrylate and/or carboxylic acid methacrylate monomer,and mixtures thereof. In one aspect, the perfume microcapsule may becoated with a deposition aid, a cationic polymer, a non-ionic polymer,an anionic polymer, or mixtures thereof. Suitable polymers may beselected from the group consisting of: polyvinylformaldehyde, partiallyhydroxylated polyvinylformaldehyde, polyvinylamine, polyethyleneimine,ethoxylated polyethyleneimine, polyvinylalcohol, polyacrylates, andcombinations thereof. In one aspect, the microcapsule may be a perfumemicrocapsule. In one aspect, one or more types of microcapsules, forexample two microcapsules types having different benefit agents may beused.

In one aspect, said perfume delivery technology may comprise an aminereaction product (ARP) or a thio reaction product. One may also use“reactive” polymeric amines and or polymeric thiols in which the amineand/or thiol functionality is pre-reacted with one or more PRMs to forma reaction product. Typically the reactive amines are primary and/orsecondary amines, and may be part of a polymer or a monomer(non-polymer). Such ARPs may also be mixed with additional PRMs toprovide benefits of polymer-assisted delivery and/or amine-assisteddelivery. Non-limiting examples of polymeric amines include polymersbased on polyalkylimines, such as polyethyleneimine (PEI), orpolyvinylamine (PVAm). Non-limiting examples of monomeric(non-polymeric) amines include hydroxyl amines, such as 2-aminoethanoland its alkyl substituted derivatives, and aromatic amines such asanthranilates. The ARPs may be premixed with perfume or added separatelyin leave-on or rinse-off applications. In another aspect, a materialthat contains a heteroatom other than nitrogen and/or sulfur, forexample oxygen, phosphorus or selenium, may be used as an alternative toamine compounds. In yet another aspect, the aforementioned alternativecompounds can be used in combination with amine compounds. In yetanother aspect, a single molecule may comprise an amine moiety and oneor more of the alternative heteroatom moieties, for example, thiols,phosphines and selenols. The benefit may include improved delivery ofperfume as well as controlled perfume release. Suitable ARPs as well asmethods of making same can be found in USPA 2005/0003980 A1 and U.S.Pat. No. 6,413,920 B1.

Suitable Fabric Softening Actives

The fluid fabric enhancer compositions disclosed herein comprise afabric softening active (“FSA”). Suitable fabric softening actives,include, but are not limited to, materials selected from the groupconsisting of quaternary ammonium compounds, amines, fatty esters,sucrose esters, silicones, dispersible polyolefins, clays,polysaccharides, fatty acids, softening oils, polymer latexes andmixtures thereof.

Non-limiting examples of water insoluble fabric care benefit agentsinclude dispersible polyethylene and polymer latexes. These agents canbe in the form of emulsions, latexes, dispersions, suspensions, and thelike. In one aspect, they are in the form of an emulsion or a latex.Dispersible polyethylenes and polymer latexes can have a wide range ofparticle size diameters (X₅₀) including but not limited to from about 1nm to about 100 μm; alternatively from about 10 nm to about 10 μm. Assuch, the particle sizes of dispersible polyethylenes and polymerlatexes are generally, but without limitation, smaller than silicones orother fatty oils.

Generally, any surfactant suitable for making polymer emulsions oremulsion polymerizations of polymer latexes can be used to make thewater insoluble fabric care benefit agents of the present invention.Suitable surfactants consist of emulsifiers for polymer emulsions andlatexes, dispersing agents for polymer dispersions and suspension agentsfor polymer suspensions. Suitable surfactants include anionic, cationic,and nonionic surfactants, or combinations thereof. In one aspect, suchsurfactants are nonionic and/or anionic surfactants. In one aspect, theratio of surfactant to polymer in the water insoluble fabric carebenefit agent is about 1:100 to about 1:2; alternatively from about 1:50to about 1:5, respectively. Suitable water insoluble fabric care benefitagents include but are not limited to the examples described below.

Quats—

Suitable quats include but are not limited to, materials selected fromthe group consisting of ester quats, amide quats, imidazoline quats,alkyl quats, amidoester quats and mixtures thereof. Suitable ester quatsinclude but are not limited to, materials selected from the groupconsisting of monoester quats, diester quats, triester quats andmixtures thereof. In one aspect, a suitable ester quat isbis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid esterhaving a molar ratio of fatty acid moieties to amine moieties of from1.85 to 1.99, an average chain length of the fatty acid moieties of from16 to 18 carbon atoms and an iodine value of the fatty acid moieties,calculated for the free fatty acid, which has an Iodine Value of between0-140, preferably 5-100, more preferably 10-80, even more preferably15-70, even more preferably 18-55, most preferably 18-25. When a softtallow quaternary ammonium compound softener is used, most preferablyrange is 25-60. In one aspect, the cis-trans-ratio of double bonds ofunsaturated fatty acid moieties of the bis (2hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester is from55:45 to 75:25, respectively. Suitable amide quats include but are notlimited to, materials selected from the group consisting of monoamidequats, diamide quats and mixtures thereof. Suitable alkyl quats includebut are not limited to, materials selected from the group consisting ofmono alkyl quats, dialkyl quats quats, trialkyl quats, tetraalkyl quatsand mixtures thereof.

Amines—

Suitable amines include but are not limited to, materials selected fromthe group consisting of amidoesteramines, amidoamines, imidazolineamines, alkyl amines, amidoester amines and mixtures thereof. Suitableester amines include but are not limited to, materials selected from thegroup consisting of monoester amines, diester amines, triester aminesand mixtures thereof. Suitable amido quats include but are not limitedto, materials selected from the group consisting of monoamido amines,diamido amines and mixtures thereof. Suitable alkyl amines include butare not limited to, materials selected from the group consisting of monoalkylamines, dialkyl amines quats, trialkyl amines, and mixturesthereof.

Silicone—

In one embodiment, the fabric softening composition comprises asilicone. Suitable levels of silicone may comprise from about 0.1% toabout 70%, alternatively from about 0.3% to about 40%, alternativelyfrom about 0.5% to about 30%, alternatively from about 1% to about 20%by weight of the composition. Useful silicones can be any siliconecomprising compound. In one embodiment, the silicone polymer is selectedfrom the group consisting of cyclic silicones, polydimethylsiloxanes,aminosilicones, cationic silicones, silicone polyethers, siliconeresins, silicone urethanes, and mixtures thereof. In one embodiment, thesilicone is a polydialkylsilicone, alternatively a polydimethyl silicone(polydimethyl siloxane or “PDMS”), or a derivative thereof. In anotherembodiment, the silicone is chosen from an aminofunctional silicone,amino-polyether silicone, alkyloxylated silicone, cationic silicone,ethoxylated silicone, propoxylated silicone, ethoxylated/propoxylatedsilicone, quaternary silicone, or combinations thereof.

In another embodiment, the silicone may be chosen from a random orblocky organosilicone polymer having the following formula:

[R₁R₂R₃SiO_(1/2)]_((j+2))[(R₄Si(X—Z)O_(2/2)]_(k)[R₄R₄SiO_(2/2)]_(m)[R₄SiO_(3/2)]_(j)

wherein:

j is an integer from 0 to about 98; in one aspect j is an integer from 0to about 48; in one aspect, j is 0;

k is an integer from 0 to about 200, in one aspect k is an integer from0 to about 50; when k=0, at least one of R₁, R₂ or R₃ is —X—Z;

m is an integer from 4 to about 5,000; in one aspect m is an integerfrom about 10 to about 4,000; in another aspect m is an integer fromabout 50 to about 2,000;

R₁, R₂ and R₃ are each independently selected from the group consistingof H, OH, C₁-C₃₂ alkyl, C₁-C₃₂ substituted alkyl, C₅-C₃₂ or C₆-C₃₂ aryl,C₅-C₃₂ or C₆-C₃₂ substituted aryl, C₆-C₃₂ alkylaryl, C₆-C₃₂ substitutedalkylaryl, C₁-C₃₂ alkoxy, C₁-C₃₂ substituted alkoxy and X—Z;

each R₄ is independently selected from the group consisting of H, OH,C₁-C₃₂ alkyl, C₁-C₃₂ substituted alkyl, C₅-C₃₂ or C₆-C₃₂ aryl, C₅-C₃₂ orC₆-C₃₂ substituted aryl, C₆-C₃₂ alkylaryl, C₆-C₃₂ substituted alkylaryl,alkoxy and C₁-C₃₂ substituted alkoxy;

each X in said alkyl siloxane polymer comprises a substituted orunsubstituted divalent alkylene radical comprising 2-12 carbon atoms, inone aspect each divalent alkylene radical is independently selected fromthe group consisting of —(CH₂)_(s)— wherein s is an integer from about 2to about 8, from about 2 to about 4; in one aspect, each X in said alkylsiloxane polymer comprises a substituted divalent alkylene radicalselected from the group consisting of: —CH₂—CH(OH)—CH₂—;—CH₂—CH₂—CH(OH)—; and

each Z is selected independently from the group consisting of

with the proviso that when Z is a quat, Q cannot be an amide, imine, orurea moiety and if Q is an amide, imine, or urea moiety, then anyadditional Q bonded to the same nitrogen as said amide, imine, or ureamoiety must be H or a C₁-C₆ alkyl.

In one aspect, said additional Q is H. For Z, A^(n−) is a suitablecharge balancing anion. In one aspect A^(n−) is selected from the groupconsisting of Cl⁻, Br⁻, I⁻, methylsulfate, toluene sulfonate,carboxylate and phosphate; and at least one Q in said organosilicone isindependently selected from

—CH₂—CH(OH)—CH₂—R₅;

and each additional Q in said organosilicone is independently selectedfrom the group comprising of H, C₁-C₃₂ alkyl, C₁-C₃₂ substituted alkyl,C₅-C₃₂ or C₆-C₃₂ aryl, C₅-C₃₂ or C₆-C₃₂ substituted aryl, C₆-C₃₂alkylaryl, C₆-C₃₂ substituted alkylaryl, —CH₂—CH(OH)—CH₂—R₅;

-   -   wherein each R₅ is independently selected from the group        consisting of H, C₁-C₃₂ alkyl, C₁-C₃₂ substituted alkyl, C₅-C₃₂        or C₆-C₃₂ aryl, C₅-C₃₂ or C₆-C₃₂ substituted aryl, C₆-C₃₂        alkylaryl, C₆-C₃₂ substituted alkylaryl, —(CHR₆—CHR₆—O—)_(w)-L        and a siloxyl residue;    -   each R₆ is independently selected from H, C₁-C₁₈ alkyl    -   each L is independently selected from —C(O)—R₇ or R₇;    -   w is an integer from 0 to about 500, in one aspect w is an        integer from about 1 to about 200; in one aspect w is an integer        from about 1 to about 50;    -   each R₇ is selected independently from the group consisting of        H; C₁-C₃₂ alkyl; C₁-C₃₂ substituted alkyl, C₅-C₃₂ or C₆-C₃₂        aryl, C₅-C₃₂ or C₆-C₃₂ substituted aryl, C₆-C₃₂ alkylaryl;        C₆-C₃₂ substituted alkylaryl and a siloxyl residue;    -   each T is independently selected from H, and

-   -    and    -   wherein each v in said organosilicone is an integer from 1 to        about 10, in one aspect, v is an integer from 1 to about 5 and        the sum of all v indices in each Q in the said organosilicone is        an integer from 1 to about 30 or from 1 to about 20 or even from        1 to about 10.

In another embodiment, the silicone may be chosen from a random orblocky organosilicone polymer having the following formula:

[R₁R₂R₃SiO_(1/2)]_((j+2))[(R₄Si(X—Z)O_(2/2)]_(k)[R₄R₄SiO_(2/2)]_(m)[R₄SiO_(3/2)]_(j)

wherein

-   -   j is an integer from 0 to about 98; in one aspect j is an        integer from 0 to about 48; in one aspect, j is 0;    -   k is an integer from 0 to about 200; when k=0, at least one of        R₁, R₂ or R₃=—X—Z, in one aspect, k is an integer from 0 to        about 50    -   m is an integer from 4 to about 5,000; in one aspect m is an        integer from about 10 to about 4,000; in another aspect m is an        integer from about 50 to about 2,000;    -   R₁, R₂ and R₃ are each independently selected from the group        consisting of H, OH, C₁-C₃₂ alkyl, C₁-C₃₂ substituted alkyl,        C₅-C₃₂ or C₆-C₃₂ aryl, C₅-C₃₂ or C₆-C₃₂ substituted aryl, C₆-C₃₂        alkylaryl, C₆-C₃₂ substituted alkylaryl, C₁-C₃₂ alkoxy, C₁-C₃₂        substituted alkoxy and X—Z;    -   each R₄ is independently selected from the group consisting of        H, OH, C₁-C₃₂ alkyl, C₁-C₃₂ substituted alkyl, C₅-C₃₂ or C₆-C₃₂        aryl, C₅-C₃₂ or C₆-C₃₂ substituted aryl, C₆-C₃₂ alkylaryl,        C₆-C₃₂ substituted alkylaryl, C₁-C₃₂ alkoxy and C₁-C₃₂        substituted alkoxy;    -   each X comprises of a substituted or unsubstituted divalent        alkylene radical comprising 2-12 carbon atoms; in one aspect        each X is independently selected from the group consisting of        —(CH₂)_(s)—O—; —CH₂—CH(OH)—CH₂—O—;

-   -   wherein each s independently is an integer from about 2 to about        8, in one aspect s is an integer from about 2 to about 4;

At least one Z in the said organosiloxane is selected from the groupconsisting of R₅;

-   -    provided that when X is

-   -    then Z=—OR₅ or

-   -   wherein A⁻ is a suitable charge balancing anion. In one aspect        A⁻ is selected from the group consisting of Cl⁻, Br⁻, I⁻,        methylsulfate, toluene sulfonate, carboxylate and phosphate and        each additional Z in said organosilicone is independently        selected from the group comprising of H, C₁-C₃₂ alkyl, C₁-C₃₂        substituted alkyl, C₅-C₃₂ or C₆-C₃₂ aryl, C₅-C₃₂ or C₆-C₃₂        substituted aryl, C₆-C₃₂ alkylaryl, C₆-C₃₂ substituted        alkylaryl, R₅,

-   -    —C(R₅)₂O—R₅; —C(R₅)₂S—R₅ and

-   -    provided that when X is

-   -    then Z=—OR₅ or

-   -   each R₅ is independently selected from the group consisting of        H; C₁-C₃₂ alkyl; C₁-C₃₂ substituted alkyl, O₅—C₃₂ or C₆-C₃₂        aryl, C₅-C₃₂ or C₆-C₃₂ substituted aryl or O₆—C₃₂ alkylaryl, or        C₆-C₃₂ substituted alkylaryl,    -   —(CHR₆—CHR₆—O—)_(w)—CHR₆—CHR₆-L and siloxyl residue wherein each        L is independently selected from —O—C(O)—R₇ or —O—R₇;

-   -   w is an integer from 0 to about 500, in one aspect w is an        integer from 0 to about 200, one aspect w is an integer from 0        to about 50;    -   each R₆ is independently selected from H or C₁-C₁₈ alkyl;    -   each R₇ is independently selected from the group consisting of        H; C₁-C₃₂ alkyl; C₁-C₃₂ substituted alkyl, C₅-C₃₂ or C₆-C₃₂        aryl, C₅-C₃₂ or C₆-C₃₂ substituted aryl, C₆-C₃₂ alkylaryl, and        C₆-C₃₂ substituted aryl, and a siloxyl residue;    -   each T is independently selected from H;

-   -   wherein each v in said organosilicone is an integer from 1 to        about 10, in one aspect, v is an integer from 1 to about 5 and        the sum of all v indices in each Z in the said organosilicone is        an integer from 1 to about 30 or from 1 to about 20 or even from        1 to about 10.

In one embodiment, the silicone is one comprising a relatively highmolecular weight. A suitable way to describe the molecular weight of asilicone includes describing its viscosity. A high molecular weightsilicone is one having a viscosity of from about 10 cSt to about3,000,000 cSt, or from about 100 cSt to about 1,000,000 cSt, or fromabout 1,000 cSt to about 600,000 cSt, or even from about 6,000 cSt toabout 300,000 cSt.

In one embodiment, the silicone comprises a blocky cationicorganopolysiloxane having the formula:

M_(w)D_(x)T_(y)Q_(z)

wherein:

M=[SiR₁R₂R₃O_(1/2)], [SiR₁R₂G₁O_(1/2)], [SiR₁G₁G₂O_(1/2)],[SiG₁G₂G₃O_(1/2)], or combinations thereof;

D=[SiR₁R₂O_(2/2)], [SiR₁G₁O_(2/2)], [SiG₁G₂O_(2/2)] or combinationsthereof;

T=[SiR₁O_(3/2)], [SiG₁O_(3/2)] or combinations thereof;

Q=[SiO_(4/2)];

w=is an integer from 1 to (2+y+2z);

x=is an integer from 5 to 15,000;

y=is an integer from 0 to 98;

z=is an integer from 0 to 98;

R₁, R₂ and R₃ are each independently selected from the group consistingof H, OH, C₁-C₃₂ alkyl, C₁-C₃₂ substituted alkyl, C₅-C₃₂ or C₆-C₃₂ aryl,C₅-C₃₂ or C₆-C₃₂ substituted aryl, C₆-C₃₂ alkylaryl, C₆-C₃₂ substitutedalkylaryl, alkoxy, C₁-C₃₂ substituted alkoxy, C₁-C₃₂ alkylamino, andC₁-C₃₂ substituted alkylamino;

at least one of M, D, or T incorporates at least one moiety G₁, G₂ orG₃; and G₁, G₂, and G₃ are each independently selected from the formula:

wherein:

X comprises a divalent radical selected from the group consisting ofC₁-C₃₂ alkylene, C₁-C₃₂ substituted alkylene, C₅-C₃₂ or C₆-C₃₂ arylene,C₅-C₃₂ or C₆-C₃₂ substituted arylene, C₆-C₃₂ arylalkylene, C₆-C₃₂substituted arylalkylene, C₁-C₃₂ alkoxy, C₁-C₃₂ substituted alkoxy,C_(r) C₃₂ alkyleneamino, C₁-C₃₂ substituted alkyleneamino, ring-openedepoxide, and ring-opened glycidyl, with the proviso that if X does notcomprise a repeating alkylene oxide moiety then X can further comprise aheteroatom selected from the group consisting of P, N and O;

each R₄ comprises identical or different monovalent radicals selectedfrom the group consisting of H, C₁-C₃₂ alkyl, C₁-C₃₂ substituted alkyl,C₅-C₃₂ or C₆-C₃₂ aryl, C₅-C₃₂ or C₆-C₃₂ substituted aryl, C₆-C₃₂alkylaryl, and C₆-C₃₂ substituted alkylaryl;

E comprises a divalent radical selected from the group consisting ofC₁-C₃₂ alkylene, C₁-C₃₂ substituted alkylene, C₅-C₃₂ or C₆-C₃₂ arylene,C₅-C₃₂ or C₆-C₃₂ substituted arylene, C₆-C₃₂ arylalkylene, C₆-C₃₂substituted arylalkylene, C₁-C₃₂ alkoxy, C₁-C₃₂ substituted alkoxy,C₁-C₃₂ alkyleneamino, C₁-C₃₂ substituted alkyleneamino, ring-openedepoxide and ring-opened glycidyl, with the proviso that if E does notcomprise a repeating alkylene oxide moiety then E can further comprise aheteroatom selected from the group consisting of P, N, and O;

E′ comprises a divalent radical selected from the group consisting ofC₁-C₃₂ alkylene, C₁-C₃₂ substituted alkylene, C₅-C₃₂ or C₆-C₃₂ arylene,O₅—C₃₂ or C₆-C₃₂ substituted arylene, C₆-C₃₂ arylalkylene, C₆-C₃₂substituted arylalkylene, C₁-C₃₂ alkoxy, C₁-C₃₂ substituted alkoxy,C₁-C₃₂ alkyleneamino, C₁-C₃₂ substituted alkyleneamino, ring-openedepoxide and ring-opened glycidyl, with the proviso that if E′ does notcomprise a repeating alkylene oxide moiety then E′ can further comprisea heteroatom selected from the group consisting of P, N, and O;

p is an integer independently selected from 1 to 50;

n is an integer independently selected from 1 or 2;

when at least one of G₁, G₂, or G₃ is positively charged, A^(−t) is asuitable charge balancing anion or anions such that the total charge, k,of the charge-balancing anion or anions is equal to and opposite fromthe net charge on the moiety G₁, G₂ or G₃; wherein t is an integerindependently selected from 1, 2, or 3; and k≦(p*2/t)+1; such that thetotal number of cationic charges balances the total number of anioniccharges in the organopolysiloxane molecule;

-   -   and wherein at least one E does not comprise an ethylene moiety.

Particularly Preferred Adjuncts for Freshening Compositions

Buffering Agent—

The freshening composition of the present invention may include abuffering agent which may be a carboxylic acid, or a dicarboxylic acidlike maleic acid, or a polybasic acid such as citric acid or polyacrylicacid. The acid may be sterically stable, and used in this compositionfor maintaining the desired pH. The buffering agent may also comprise abase such as triethanolamine, or the salt of an organic acid such assodium citrate. The freshening composition may have a pH from about 3 toabout 8, alternatively from about 4 to about 7, alternatively from about5 to about 8, alternatively from about 6 to about 8, alternatively about6 to about 7, alternatively about 7, alternatively about 6.5. Carboxylicacids such as citric acid may act as metal ion chelants and can formmetallic salts with low water solubility. As such, in some embodiments,the freshening composition is essentially free of citric acids. Thebuffer can be alkaline, acidic or neutral.

Other suitable buffering agents for freshening compositions of thepresent invention include biological buffering agents. Some examples arenitrogen-containing materials, sulfonic acid buffers like3-(N-morpholino)propanesulfonic acid (MOPS) orN-(2-Acetamido)-2-aminoethanesulfonic acid (ACES), which have a nearneutral 6.2 to 7.5 pKa and provide adequate buffering capacity at aneutral pH. Other examples are amino acids such as lysine or loweralcohol amines like mono-, di-, and tri-ethanolamine. Othernitrogen-containing buffering agents are tri(hydroxymethyl)amino methane(HOCH2)3CNH3 (TRIS), 2-amino-2-ethyl-1,3-propanediol,2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanol, disodiumglutamate, N-methyl diethanolamide, 2-dimethylamino-2-methylpropanol(DMAMP), 1, 3-bis(methylamine)-cyclohexane, 1,3-diamino-propanolN,N′-tetra-methyl-1,3-diamino-2-propanol, N,N-bis(2-hydroxyethyl)glycine(bicine) and N-tris (hydroxymethyl)methyl glycine (tricine). Mixtures ofany of the above are also acceptable.

The freshening compositions may contain at least about 0%, alternativelyat least about 0.001%, alternatively at least about 0.01%, by weight ofthe composition, of a buffering agent. The composition may also containno more than about 1%, alternatively no more than about 0.75%,alternatively no more than about 0.5%, by weight of the composition, ofa buffering agent.

Solubilizer—

The freshening composition of the present invention may contain asolubilizing aid to solubilize any excess hydrophobic organic materials,particularly some malodor reduction materials of the current invention,perfume materials, and also optional ingredients (e.g., insect repellingagent, antioxidant, etc.) which can be added to the composition, thatare not readily soluble in the composition, to form a clear translucentsolution. A suitable solubilizing aid is a surfactant, such as ano-foaming or low-foaming surfactant. Suitable surfactants are nonionicsurfactants, cationic surfactants, amphoteric surfactants, zwitterionicsurfactants, and mixtures thereof.

In some embodiments, the freshening composition contains nonionicsurfactants, cationic surfactants, and mixtures thereof. In oneembodiment, the freshening composition contains ethoxylated hydrogenatedcastor oil. One type of suitable hydrogenated castor oil that may beused in the present composition is sold as Basophor™, available fromBASF.

Freshening compositions containing anionic surfactants and/or detergentsurfactants may make fabrics susceptible to soiling and/or leaveunacceptable visible stains on fabrics as the solution evaporates off ofthe fabric. In some embodiments, the freshening composition is free ofanionic surfactants and/or detergent surfactants.

When the solubilizing agent is present, it is typically present at alevel of from about 0.01% to about 3%, alternatively from about 0.05% toabout 1%, alternatively from about 0.01% to about 0.05%, by weight ofthe freshening composition.

Antimicrobial Compounds—

The freshening composition of the present invention may include aneffective amount of a compound for reducing microbes in the air or oninanimate surfaces. Antimicrobial compounds are effective on gramnegative and gram positive bacteria and fungi typically found on indoorsurfaces that have contacted human skin or pets such as couches,pillows, pet bedding, and carpets. Such microbial species includeKlebsiella pneumoniae, Staphylococcus aureus, Aspergillus niger,Klebsiella pneumoniae, Streptococcus pyogenes, Salmonella choleraesuis,Escherichia coli, Trichophyton mentagrophytes, and Pseudomonasaeruginosa. In some embodiments, the antimicrobial compounds are alsoeffective on viruses such H1-N1, Rhinovirus, Respiratory Syncytial,Poliovirus Type 1, Rotavirus, Influenza A, Herpes simplex types 1 & 2,Hepatitis A, and Human Coronavirus.

Antimicrobial compounds suitable in the freshening composition of thepresent invention can be any organic material which will not causedamage to fabric appearance (e.g., discoloration, coloration such asyellowing, bleaching). Water-soluble antimicrobial compounds includeorganic sulfur compounds, halogenated compounds, cyclic organic nitrogencompounds, low molecular weight aldehydes, quaternary compounds,dehydroacetic acid, phenyl and phenoxy compounds, or mixtures thereof.

In one embodiment, a quaternary compound is used. Examples ofcommercially available quaternary compounds suitable for use in thefreshening composition are Barquat available from Lonza Corporation; anddidecyl dimethyl ammonium chloride quat under the trade name Bardac®2250 from Lonza Corporation.

The antimicrobial compound may be present in an amount from about 500ppm to about 7000 ppm, alternatively about 1000 ppm to about 5000 ppm,alternatively about 1000 ppm to about 3000 ppm, alternatively about 1400ppm to about 2500 ppm, by weight of the freshening composition.

Preservatives—

The freshening composition of the present invention may include apreservative. The preservative is included in the present invention inan amount sufficient to prevent spoilage or prevent growth ofinadvertently added microorganisms for a specific period of time, butnot sufficient enough to contribute to the odor neutralizing performanceof the freshening composition. In other words, the preservative is notbeing used as the antimicrobial compound to kill microorganisms on thesurface onto which the composition is deposited in order to eliminateodors produced by microorganisms. Instead, it is being used to preventspoilage of the freshening composition in order to increase theshelf-life of the composition.

The preservative can be any organic preservative material which will notcause damage to fabric appearance, e.g., discoloration, coloration,bleaching. Suitable water-soluble preservatives include organic sulfurcompounds, halogenated compounds, cyclic organic nitrogen compounds, lowmolecular weight aldehydes, parabens, propane diol materials,isothiazolinones, quaternary compounds, benzoates, low molecular weightalcohols, dehydroacetic acid, phenyl and phenoxy compounds, or mixturesthereof. Non-limiting examples of commercially available water-solublepreservatives for use in the present invention include a mixture ofabout 77% 5-chloro-2-methyl-4-isothiazolin-3-one and about 23%2-methyl-4-isothiazolin-3-one, a broad spectrum preservative availableas a 1.5% aqueous solution under the trade name Kathon® CG by Rohm andHaas Co.; 5-bromo-5-nitro-1,3-dioxane, available under the tradenameBronidox L® from Henkel; 2-bromo-2-nitropropane-1,3-diol, availableunder the trade name Bronopol® from Inolex; 1,1′-hexamethylenebis(5-(p-chlorophenyl)biguanide), commonly known as chlorhexidine, andits salts, e.g., with acetic and digluconic acids; a 95:5 mixture of1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione and3-butyl-2-iodopropynyl carbamate, available under the trade name GlydantPlus® from Lonza;N-[1,3-bis(hydroxymethyl)2,5-dioxo-4-imidazolidinyl]-N,N′-bis(hydroxy-methyl)urea, commonly known as diazolidinyl urea, available under the tradename Germall® II from Sutton Laboratories, Inc.;N,N″-methylenebis{N′-[1-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]urea},commonly known as imidazolidinyl urea, available, e.g., under the tradename Abiol® from 3V-Sigma, Unicide U-13® from Induchem, Germall 115®from Sutton Laboratories, Inc.; polymethoxy bicyclic oxazolidine,available under the trade name Nuosept® C from Hüls America;formaldehyde; glutaraldehyde; polyaminopropyl biguanide, available underthe trade name Cosmocil CQ® from ICI Americas, Inc., or under the tradename Mikrokill® from Brooks, Inc; dehydroacetic acid; andbenzsiothiazolinone available under the trade name Koralone™ B-119 fromRohm and Hass Corporation.

Suitable levels of preservative are from about 0.0001% to about 0.5%,alternatively from about 0.0002% to about 0.2%, alternatively from about0.0003% to about 0.1%, by weight of the freshening composition.

Wetting Agents—

The freshening composition may include a wetting agent that provides alow surface tension that permits the composition to spread readily andmore uniformly on hydrophobic surfaces like polyester and nylon. It hasbeen found that the aqueous solution, without such a wetting agent willnot spread satisfactorily. The spreading of the composition also allowsit to dry faster, so that the treated material is ready to use sooner.Furthermore, a composition containing a wetting agent may penetratehydrophobic, oily soil better for improved malodor neutralization. Acomposition containing a wetting agent may also provide improved“in-wear” electrostatic control. For concentrated compositions, thewetting agent facilitates the dispersion of many actives such asantimicrobial actives and perfumes in the concentrated aqueouscompositions.

Non-limiting examples of wetting agents include block copolymers ofethylene oxide and propylene oxide. Suitable blockpolyoxyethylene-polyoxypropylene polymeric surfactants include thosebased on ethylene glycol, propylene glycol, glycerol, trimethylolpropaneand ethylenediamine as the initial reactive hydrogen compound. Polymericcompounds made from a sequential ethoxylation and propoxylation ofinitial compounds with a single reactive hydrogen atom, such as C12-18aliphatic alcohols, are not generally compatible with the cyclodextrin.Certain of the block polymer surfactant compounds designated Pluronic®and Tetronic® by the BASF-Wyandotte Corp., Wyandotte, Mich., are readilyavailable. Nonlimiting examples of wetting agents of this type aredescribed in U.S. Pat. No. 5,714,137 and include the Silwet® surfactantsavailable from Momentive Performance Chemical, Albany, N.Y. ExemplarySilwet surfactants are as presented in Table 8 which may be used aloneor in combinations of one another.

TABLE 8 Name L-7608 L-7607 L-77 L-7605 L-7604 L-7600 L-7657 L-7602Average MW 600 1000 600 6000 4000 4000 5000 3000

In another aspect of the invention freshening fabric is a restoration ofthe fabric such as its surface appearance (reduction of wrinkling,improved color appearance, improved or restored fabric shape). Adjunctingredients that help restore fabric appearance are selected from: watersoluble or miscible quaternary ammonium surfactants and water insolubleoil components together with surfactants, emulsifiers, and solventsneeded to form a composition that is stable and does not separate. Somenon-limiting preferred emulsifiers are sorbitan esters and sorbitanesters modified with alkylene oxides, such as Tween® 20 (polyoxyethylene(20)sorbitan monolaurate, branched surfactants, like Guerbet alcohols oralkylene oxide modified Guerget alcohols such as Lutensol® XL 70(Oxirane, 2-methyl-, polymer with oxirane, mono(2-propylheptyl) ether,BASF). It is optional but preferred to have a wetting agent in thisaspect of the invention. Wetting agents aid in spreading components andin reducing foaming of the composition during spraying. Some preferredwetting agents include the class of wetting agents known in the art assuperwetters. Not to be bound by theory, superwetters pack veryefficiently at surfaces resulting in an extremely low equilibriumsurface tension. Non-limiting examples of such surfactants includeSurfynols® like Surfynol® 465 and Surfynol® 104PG 50 (Dow Chemicals).

Water Soluble or Miscible Quaternary Ammonium Surfactant:

Typically, minimum levels of the water soluble quat included in thecompositions of the present invention are at least about 0.01%,preferably at least about 0.05%, more preferably at least about 0.1%even more preferably at least about 0.2% by weight, based on the totalweight of the composition. Typically maximum levels of water solublequaternary agent included in the composition are up to about 20%,preferably less than about 10%, and more preferably less than about 3%based on the total weight of the composition. Typically, the agent ispresent in the composition in an amount of about 0.2% to about 1.0%.

Specifically, the preferred water soluble quaternary compounds aredialkly quaternary surfactant compounds. Suitable quaternary surfactantsinclude, but are not limited to, quaternary ammonium surfactants havingthe formula:

wherein R₁ and R₂ are individually selected from the group consisting ofC₁-C₄ alkyl, C₁-C₄ hydroxy alkyl, benzyl, and —(C₂H₄O)_(x)H where x hasa value from about 2 to about 5; X is an anion; and (1) R₃ and R₄ areeach a C₆-C₁₄ alkyl or (2) R₃ is a C₆-C₁₈ alkyl, and R₄ is selected fromthe group consisting of C₁-C₁₀ alkyl, C₁-C₁₀ hydroxy alkyl, benzyl, and—(C₂H₄O)_(x)H where x has a value from 2 to 5. A preferred asymmetricquaternary compounds for this invention are compounds where R3 and R4are not identical, and preferably one is branched and the other one islinear.

An example of a preferred asymmetric quaternary compound is ARQUADHTL8-MS where X is a methyl sulfate ion, R1 and R2 are methyl groups, R3is a hydrogenated tallow group with <5% mono unsaturation, and R4 is a2-ethylhexyl group. ARQUAD HTL8-MS is available from Akzo Nobel Chemicalof Arnhem, Netherlands.

An example of a suitable symmetric quaternary compound is UNIQUAT 22c50where X is a carbonate and bicarbonate, R1 and R2 are methyl groups, R3and R4 are C10 alkyl groups. UNIQUAT 22c50 is a registered trademark ofLonza and in North America is available thru Lonza Incorporated ofAllendale, N.J.

Another example of a suitable water soluble quaternary compound isBARQUAT CME-35 which is N-Cetyl Ethyl Morpholinium Ethosulfate availablefrom Lonza and having the following structure:

Oil Component—

The oil component of the present invention represents a substantiallywater insoluble material that is incorporated into the composition byway of a microemulsion. The said oil component is a non-perfume rawmaterial and a non-malodor reduction material. Typically the minimumlevels of the oil component included in the composition are at leastabout 0.001%, preferably at least about 0.005%, more preferably at leastabout 0.01%, and typically maximum levels of oil components are up toabout 5%, preferably less than about 3%, more preferably less than 1.5;with typical levels being in the range of about 0.05% to about 1%. Theoil component can be a single component or a mixture and usuallyrepresents the incorporation of some benefit agent into the compositionsuch as the nonlimiting example benefits softness or wrinklereduction/release. Typically the oil component comprises substituted orunsubstituted hydrocarbon(s) and the like. For spray products it ispreferred that the oil component or mix be a liquid at room temperaturefor ease of incorporation into the composition and less potential fornozzle clogging on drying.

The oil components of the present invention are substantially waterinsoluble and form a microemulsion. Substantially water insoluble meansthe log P of the ingredients are greater than about 1. A log P of about1 indicates that the component would tend to partition into octanolabout 10 times more than water. Some preferred, but non-limiting,components in the oil mixture are branched hydrocarbons and perfumeswhen perfumes are used.

Aqueous Carrier—

The freshening composition of the present invention may include anaqueous carrier. The aqueous carrier which is used may be distilled,deionized, or tap water. Water may be present in any amount for thecomposition to be an aqueous solution. In some embodiments, water may bepresent in an amount of about 85% to 99.5%, alternatively about 90% toabout 99.5%, alternatively about 92% to about 99.5%, alternatively about95%, by weight of said freshening composition. Water containing a smallamount of low molecular weight monohydric alcohols, e.g., ethanol,methanol, and isopropanol, or polyols, such as ethylene glycol andpropylene glycol, can also be useful. However, the volatile lowmolecular weight monohydric alcohols such as ethanol and/or isopropanolshould be limited since these volatile organic compounds will contributeboth to flammability problems and environmental pollution problems. Ifsmall amounts of low molecular weight monohydric alcohols are present inthe composition of the present invention due to the addition of thesealcohols to such things as perfumes and as stabilizers for somepreservatives, the level of monohydric alcohol may about 1% to about 5%,alternatively less than about 6%, alternatively less than about 3%,alternatively less than about 1%, by weight of the fresheningcomposition.

Other Ingredients—

The freshening composition may include perfume raw materials that solelyprovide a hedonic benefit (i.e. that do not neutralize malodors yetprovide a pleasant fragrance). Suitable perfumes are disclosed in U.S.Pat. No. 6,248,135, which is incorporated in its entirety by reference.For example, the freshening composition may include a mixture ofvolatile aldehydes for neutralizing a malodor and hedonic perfumealdehydes. Where perfumes, other than the volatile aldehydes in themalodor control component, are formulated into the fresheningcomposition of the present invention, the total amount of perfumes andvolatile aldehydes in the malodor control component may be from about0.015% to about 1%, alternatively from about 0.01% to about 0.5%,alternatively from about 0.015% to about 0.3%, by weight of thefreshening composition.

The freshening composition may also include diluents. Exemplary diluentsinclude dipropylene glycol methyl ether, and3-methoxy-3-methyl-1-butanol, and mixtures thereof.

Optionally, adjuvants can be added to the freshening composition hereinfor their known purposes. Such adjuvants include, but are not limitedto, water soluble metallic salts, including zinc salts, copper salts,and mixtures thereof; antistatic agents; insect and moth repellingagents; colorants; antioxidants; aromatherapy agents and mixturesthereof.

The freshening composition may include other malodor reducingtechnologies in addition to the malodor reduction composition of thecurrent invention. This may include, without limitation, aminefunctional polymers, metal ions, cyclodextrins, cyclodextrinderivatives, polyols, oxidizing agents, activated carbon, andcombinations thereof.

Particularly Preferred Adjuncts for Personal Care Compositions

While not essential for the purposes of the present invention, thenon-limiting list of adjuncts illustrated hereinafter are suitable foruse in the instant compositions and may be desirably incorporated incertain aspects of the invention, for example to assist or enhanceperformance.

A variety of optional ingredients can also be added to personal carecompositions. Optional ingredients can include, but are not limited to,structurants, humectants, fatty acids, inorganic salts, and otherantimicrobial agents or actives.

A personal care composition can also include hydrophilic structurantssuch as carbohydrate structurants and gums. Some suitable carbohydratestructurants include raw starch (corn, rice, potato, wheat, and thelike) and pregelatinized starch. Some suitable gums include carrageenanand xanthan gum. A personal care composition can include from about 0.1%to about 30%, from about 2% to about 25%, or from about 4% to about 20%,by weight of the personal care composition, of a carbohydratestructurant.

A personal care composition can also include one or more humectants.Examples of such humectants can include polyhydric alcohols. Further,humectants such as glycerin can be included the personal carecomposition as a result of production or as an additional ingredient.For example, glycerin can be a by-product after saponification of thepersonal care composition. Including additional humectant can result ina number of benefits such as improvement in hardness of the personalcare composition, decreased water activity of the personal carecomposition, and reduction of a weight loss rate of the personal carecomposition over time due to water evaporation.

A personal care composition can include inorganic salts. Inorganic saltscan help to maintain a particular water content or level of the personalcare composition and improve hardness of the personal care composition.The inorganic salts can also help to bind the water in the personal carecomposition to prevent water loss by evaporation or other means. Apersonal care composition can optionally include from about 0.01% toabout 15%, from about 1% to about 12%, or from about 2.5% to about10.5%, by weight of the personal care composition, of inorganic salt.Examples of suitable inorganic salts can include magnesium nitrate,trimagnesium phosphate, calcium chloride, sodium carbonate, sodiumaluminum sulfate, disodium phosphate, sodium polymetaphosphate, sodiummagnesium succinate, sodium tripolyphosphate, aluminum sulfate, aluminumchloride, aluminum chlorohydrate, aluminum-zirconium trichiorohydrate,aluminum-zirconium trichlorohydrate glycine complex, zinc sulfate,ammonium chloride, ammonium phosphate, calcium acetate, calcium nitrate,calcium phosphate, calcium sulfate, ferric sulfate, magnesium chloride,magnesium sulfate, and tetrasodium pyrophosphate.

A personal care composition can include one or more additionalantibacterial agents that can serve to further enhance antimicrobialeffectiveness of the personal care composition. A personal carecomposition can include, for example, from about 0.001% to about 2%,from about 0.01% to about 1.5%, or from about 0.1% to about 1%, byweight of the personal care composition, of additional antibacterialagent(s). Examples of suitable antibacterial agents can includecarbanilides, triclocarban (also known as trichlorocarbanilide),triclosan, a halogenated diphenylether available as DP-300 fromCiba-Geigy, hexachlorophene, 3,4,5-tribromosalicylanilide, and salts of2-pyridinethiol-1-oxide, salicylic acid, and other organic acids. Othersuitable antibacterial agents are described in U.S. Pat. No. 6,488,943.

Scalp Active Material—

In an embodiment of the present invention, the personal care compositionmay comprise a scalp active material, which may be an anti-dandruffactive. In an embodiment, the anti-dandruff active is selected from thegroup consisting of: pyridinethione salts; zinc carbonate; azoles, suchas ketoconazole, econazole, and elubiol; selenium sulfide; particulatesulfur; keratolytic agents such as salicylic acid; and mixtures thereof.In a further embodiment, the anti-dandruff active may be ananti-dandruff particulate. In an embodiment, the anti-dandruffparticulate is a pyridinethione salt. Such anti-dandruff particulateshould be physically and chemically compatible with the components ofthe composition, and should not otherwise unduly impair productstability, aesthetics or performance.

Pyridinethione particulates are suitable particulate anti-dandruffactives for use in composition of the present invention. In anembodiment, the anti-dandruff active is a 1-hydroxy-2-pyridinethionesalt and is in particulate form. In an embodiment, the concentration ofpyridinethione anti-dandruff particulate ranges from about 0.01% toabout 5%, by weight of the composition, or from about 0.1% to about 3%,or from about 0.1% to about 2%. In an embodiment, the pyridinethionesalts are those formed from heavy metals such as zinc, tin, cadmium,magnesium, aluminium and zirconium, generally zinc, typically the zincsalt of 1-hydroxy-2-pyridinethione (known as “zinc pyridinethione” or“ZPT”; zinc pyrithione), commonly 1-hydroxy-2-pyridinethione salts inplatelet particle form. In an embodiment, the 1-hydroxy-2-pyridinethionesalts in platelet particle form have an average particle size of up toabout 20 microns, or up to about 5 microns, or up to about 2.5 microns.Salts formed from other cations, such as sodium, may also be suitable.

In an embodiment, in addition to the anti-dandruff active selected frompolyvalent metal salts of pyrithione, the composition further comprisesone or more anti-fungal and/or anti-microbial actives. In an embodiment,the anti-microbial active is selected from the group consisting of: coaltar, sulfur, fcharcoal, whitfield's ointment, castellani's paint,aluminum chloride, gentian violet, octopirox (piroctone olamine),ciclopirox olamine, undecylenic acid and its metal salts, potassiumpermanganate, selenium sulfide, sodium thiosulfate, propylene glycol,oil of bitter orange, urea preparations, griseofulvin,8-hydroxyquinoline ciloquinol, thiobendazole, thiocarbamates,haloprogin, polyenes, hydroxypyridone, morpholine, benzylamine,allylamines (such as terbinafine), tea tree oil, clove leaf oil,coriander, palmarosa, berberine, thyme red, cinnamon oil, cinnamicaldehyde, citronellic acid, hinokitol, ichthyol pale, Sensiva SC-50,Elestab HP-100, azelaic acid, lyticase, iodopropynyl butylcarbamate(IPBC), isothiazalinones such as octyl isothiazalinone, and azoles, andmixtures thereof. In an embodiment, the anti-microbial is selected fromthe group consisting of: itraconazole, ketoconazole, selenium sulfide,coal tar, and mixtures thereof.

In an embodiment, the azole anti-microbials is an imidazole selectedfrom the group consisting of: benzimidazole, benzothiazole, bifonazole,butaconazole nitrate, climbazole, clotrimazole, croconazole,eberconazole, econazole, elubiol, fenticonazole, fluconazole,flutimazole, isoconazole, ketoconazole, lanoconazole, metronidazole,miconazole, neticonazole, omoconazole, oxiconazole nitrate,sertaconazole, sulconazole nitrate, tioconazole, thiazole, and mixturesthereof, or the azole anti-microbials is a triazole selected from thegroup consisting of: terconazole, itraconazole, and mixtures thereof.When present in the composition, the azole anti-microbial active isincluded in an amount of from about 0.01% to about 5%, or from about0.1% to about 3%, or from about 0.3% to about 2%, by total weight of thecomposition. In an embodiment, the azole anti-microbial active isketoconazole. In an embodiment, the sole anti-microbial active isketoconazole.

The present invention may also comprise a combination of anti-microbialactives. In an embodiment, the combination of anti-microbial active isselected from the group of combinations consisting of: octopirox andzinc pyrithione, pine tar and sulfur, salicylic acid and zincpyrithione, salicylic acid and elubiol, zinc pyrithione and elubiol,zinc pyrithione and climbasole, octopirox and climbasole, salicylic acidand octopirox, and mixtures thereof.

In an embodiment, the composition comprises an effective amount of azinc-containing layered material. In an embodiment, the compositioncomprises from about 0.001% to about 10%, or from about 0.01% to about7%, or from about 0.1% to about 5% of a zinc-containing layeredmaterial, by total weight of the composition. Zinc-containing layeredmaterials may be those with crystal growth primarily occurring in twodimensions. It is conventional to describe layer structures as not onlythose in which all the atoms are incorporated in well-defined layers,but also those in which there are ions or molecules between the layers,called gallery ions (A. F. Wells “Structural Inorganic Chemistry”Clarendon Press, 1975). Zinc-containing layered materials (ZLMs) mayhave zinc incorporated in the layers and/or be components of the galleryions. The following classes of ZLMs represent relatively common examplesof the general category and are not intended to be limiting as to thebroader scope of materials which fit this definition.

Many ZLMs occur naturally as minerals. In an embodiment, the ZLM isselected from the group consisting of: hydrozincite (zinc carbonatehydroxide), basic zinc carbonate, aurichalcite (zinc copper carbonatehydroxide), rosasite (copper zinc carbonate hydroxide), and mixturesthereof. Related minerals that are zinc-containing may also be includedin the composition. Natural ZLMs can also occur wherein anionic layerspecies such as clay-type minerals (e.g., phyllosilicates) containion-exchanged zinc gallery ions. All of these natural materials can alsobe obtained synthetically or formed in situ in a composition or during aproduction process.

Another common class of ZLMs, which are often, but not always,synthetic, is layered double hydroxides. In an embodiment, the ZLM is alayered double hydroxide conforming to the formula [M²⁺ _(1-x)M³⁺_(x)(OH)₂]^(x+) A^(m−) _(x/m).nH₂O wherein some or all of the divalentions (M²⁺) are zinc ions. Yet another class of ZLMs can be preparedcalled hydroxy double salts

In an embodiment, the ZLM is a hydroxy double salt conforming to theformula [M²⁺ _(1-x)M²⁺ _(1+x)(OH)_(3(1−y))]⁺ A^(n−) _((1=3y)/n).nH₂Owhere the two metal ions (M²⁺) may be the same or different. If they arethe same and represented by zinc, the formula simplifies to[Zn_(1+x)(OH)₂]^(2x+) 2x A⁻.nH₂O. This latter formula represents (wherex=. 0.4) materials such as zinc hydroxychloride and zinc hydroxynitrate.In an embodiment, the ZLM is zinc hydroxychloride and/or zinchydroxynitrate. These are related to hydrozincite as well wherein adivalent anion replace the monovalent anion. These materials can also beformed in situ in a composition or in or during a production process.

In an embodiment, the composition comprises basic zinc carbonate.Commercially available sources of basic zinc carbonate include ZincCarbonate Basic (Cater Chemicals: Bensenville, Ill., USA), ZincCarbonate (Shepherd Chemicals: Norwood, Ohio, USA), Zinc Carbonate (CPSUnion Corp.: New York, N.Y., USA), Zinc Carbonate (Elementis Pigments:Durham, UK), and Zinc Carbonate AC (Bruggemann Chemical: Newtown Square,Pa., USA). Basic zinc carbonate, which also may be referred tocommercially as “Zinc Carbonate” or “Zinc Carbonate Basic” or “ZincHydroxy Carbonate”, is a synthetic version consisting of materialssimilar to naturally occurring hydrozincite. The idealized stoichiometryis represented by Zn₅(OH)₆(CO₃)₂ but the actual stoichiometric ratioscan vary slightly and other impurities may be incorporated in thecrystal lattice.

In embodiments having a zinc-containing layered material and apyrithione or polyvalent metal salt of pyrithione, the ratio ofzinc-containing layered material to pyrithione or a polyvalent metalsalt of pyrithione is from about 5:100 to about 10:1, or from about 2:10to about 5:1, or from about 1:2 to about 3:1.

Liquid Personal Care Compositions

Exemplary liquid rinse-off personal care compositions can include anaqueous carrier, which can be present at a level of from about 5% toabout 95%, or from about 60% to about 85%. The aqueous carrier maycomprise water, or a miscible mixture of water and organic solvent.Non-aqueous carrier materials can also be employed.

Such rinse-off personal care compositions can include one or moredetersive surfactants. The detersive surfactant component can beincluded to provide cleaning performance to the product. The detersivesurfactant component in turn comprises anionic detersive surfactant,zwitterionic or amphoteric detersive surfactant, or a combinationthereof. A representative, non-limiting, list of anionic surfactantsincludes anionic detersive surfactants for use in the compositions caninclude ammonium lauryl sulfate, ammonium laureth sulfate, triethylaminelauryl sulfate, triethylamine laureth sulfate, triethanolamine laurylsulfate, triethanolamine laureth sulfate, monoethanolamine laurylsulfate, monoethanolamine laureth sulfate, diethanolamine laurylsulfate, diethanolamine laureth sulfate, lauric monoglyceride sodiumsulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium laurylsulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodiumlauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoylsulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroylsulfate, potassium cocoyl sulfate, potassium lauryl sulfate,triethanolamine lauryl sulfate, triethanolamine lauryl sulfate,monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodiumtridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodiumcocoyl isethionate and combinations thereof. In one example, the anionicsurfactant can be sodium lauryl sulfate or sodium laureth sulfate. Theconcentration of the anionic surfactant component in the product can besufficient to provide a desired cleaning and/or lather performance, andgenerally ranges from about 2% to about 50%.

Amphoteric detersive surfactants suitable for use in the rinse-offpersonal care compositions are well known in the art, and include thosesurfactants broadly described as derivatives of aliphatic secondary andtertiary amines in which an aliphatic radical can be straight orbranched chain and wherein an aliphatic substituent can contain fromabout 8 to about 18 carbon atoms such that one carbon atom can containan anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate,phosphate, or phosphonate. Examples of compounds falling within thisdefinition can be sodium 3-dodecyl-aminopropionate, sodium3-dodecylaminopropane sulfonate, sodium lauryl sarcosinate,N-alkyltaurines such as the one prepared by reacting dodecylamine withsodium isethionate according to the teaching of U.S. Pat. No. 2,658,072,N-higher alkyl aspartic acids such as those produced according to theteaching of U.S. Pat. No. 2,438,091, and products described in U.S. Pat.No. 2,528,378. Other examples of amphoteric surfactants can includesodium lauroamphoacetate, sodium cocoamphoactetate, disodiumlauroamphoacetate disodium cocodiamphoacetate, and mixtures thereof.Amphoacetates and diamphoacetates can also be used.

Zwitterionic detersive surfactants suitable for use in the rinse-offpersonal care compositions are well known in the art, and include thosesurfactants broadly described as derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which aliphaticradicals can be straight or branched chains, and wherein an aliphaticsubstituent can contain from about 8 to about 18 carbon atoms such thatone carbon atom can contain an anionic group, e.g., carboxy, sulfonate,sulfate, phosphate, or phosphonate. Other zwitterionic surfactants caninclude betaines, including cocoamidopropyl betaine.

The liquid rinse off personal care composition can comprise one or morephases. Such personal care compositions can include a cleansing phaseand/or a benefit phase (i.e., a single- or multi-phase composition).Each of a cleansing phase or a benefit phase can include variouscomponents. The cleansing phase and the benefit phase can be blended,separate, or a combination thereof. The cleansing phase and the benefitphase can also be patterned (e.g. striped).

The cleansing phase of a personal care composition can include at leastone surfactant. The cleansing phase can be an aqueous structuredsurfactant phase and constitute from about 5% to about 20%, by weight ofthe personal care composition. Such a structured surfactant phase caninclude sodium trideceth(n) sulfate, hereinafter STnS, wherein n candefine average moles of ethoxylation. n can range, for example, fromabout 0 to about 3; from about 0.5 to about 2.7, from about 1.1 to about2.5, from about 1.8 to about 2.2, or n can be about 2. When n can beless than 3, STnS can provide improved stability, improved compatibilityof benefit agents within the personal care compositions, and increasedmildness of the personal care compositions as disclosed in U.S.Pre-Grant Publication No. 2010/009285 A1.

The cleansing phase can also comprise at least one of an amphotericsurfactant and a zwitterionic surfactant. Suitable amphoteric orzwitterionic surfactants (in addition to those cited herein) caninclude, for example, those described in U.S. Pat. No. 5,104,646 andU.S. Pat. No. 5,106,609.

A cleansing phase can comprise a structuring system. A structuringsystem can comprise, optionally, a non-ionic emulsifier, optionally,from about 0.05% to about 5%, by weight of the personal carecomposition, of an associative polymer; and an electrolyte.

The personal care composition can optionally be free of sodium laurylsulfate, hereinafter SLS, and can comprise at least a 70% lamellarstructure. However, the cleansing phase could comprise at least onesurfactant, wherein the at least one surfactant includes SLS. Suitableexamples of SLS are described in U.S. Pre-Grant Publication No.2010/0322878 A1.

Rinse-off personal care compositions can also include a benefit phase.The benefit phase can be hydrophobic and/or anhydrous. The benefit phasecan also be substantially free of surfactant. A benefit phase can alsoinclude a benefit agent. In particular, a benefit phase can comprisefrom about 0.1% to about 50% benefit agent by weight of the personalcare composition. The benefit phase can alternatively comprise lessbenefit agent, for example, from about 0.5% to about 20% benefit agent,by weight of the personal care composition. Examples of suitable benefitagents can include petrolatum, glyceryl monooleate, mineral oil, naturaloils, and mixtures thereof. Additional examples of benefit agents caninclude water insoluble or hydrophobic benefit agents. Other suitablebenefit agents are described in U.S. Pre-Grant Publication No.2012/0009285 A1.

Non-limiting examples of glycerides suitable for use as hydrophobic skinbenefit agents herein can include castor oil, safflower oil, corn oil,walnut oil, peanut oil, olive oil, cod liver oil, almond oil, avocadooil, palm oil, sesame oil, vegetable oils, sunflower seed oil, soybeanoil, vegetable oil derivatives, coconut oil and derivatized coconut oil,cottonseed oil and derivatized cottonseed oil, jojoba oil, cocoa butter,and combinations thereof.

Non-limiting examples of alkyl esters suitable for use as hydrophobicskin benefit agents herein can include isopropyl esters of fatty acidsand long chain esters of long chain (i.e. C10-C24) fatty acids, e.g.,cetyl ricinoleate, non-limiting examples of which can include isopropylpalmitate, isopropyl myristate, cetyl riconoleate, and stearylriconoleate. Other example can include hexyl laurate, isohexyl laurate,myristyl myristate, isohexyl palmitate, decyl oleate, isodecyl oleate,hexadecyl stearate, decyl stearate, isopropyl isostearate, diisopropyladipate, diisohexyl adipate, dihexyldecyl adipate, diisopropyl sebacate,acyl isononanoate lauryl lactate, myristyl lactate, cetyl lactate, andcombinations thereof.

Non-limiting examples of polyglycerin fatty acid esters suitable for useas hydrophobic skin benefit agents herein can include decaglyceryldistearate, decaglyceryl diisostearate, decaglyceryl monomyriate,decaglyceryl monolaurate, hexaglyceryl monooleate, and combinationsthereof.

The rinse-off personal care composition can be applied by a variety ofmeans, including by rubbing, wiping or dabbing with hands or fingers, orby means of an implement and/or delivery enhancement device.Non-limiting examples of implements include a sponge or sponge-tippedapplicator, a mesh shower puff, a swab, a brush, a wipe (e.g., washcloth), a loofah, and combinations thereof. Non-limiting examples ofdelivery enhancement devices include mechanical, electrical, ultrasonicand/or other energy devices. Employment of an implement or device canhelp delivery of the particulate antimicrobial agent to target regions,such as, for example, hair follicles and undulations that can exist inthe underarm. The rinse-off care product can be sold together with suchan implement or device. Alternatively, an implement or device can besold separately but contain indicium to indicate usage with a rinse-offcare product. Implements and delivery devices can employ replaceableportions (e.g., the skin interaction portions), which can be soldseparately or sold together with the rinse-off care product in a kit.

Solid Personal Care Compositions

As noted herein, personal care compositions can take on numerous forms.One suitable form is that of a solid personal care composition. Solidcompositions can take many forms like powder, pellets, bars, etc. Theseforms will generally be described herein as bar soap, but it should beunderstood that the solid composition could be in another form or shape.One example of a bar soap personal care composition can include fromabout 0.1% to about 35%, by weight of the personal care composition, ofwater, from about 45% to about 99%, by weight of the personal carecomposition, of soap, and from about 0.01% to about 5%, by weight of thepersonal care composition, of a particulate antimicrobial agent. Anothersuitable antimicrobial bar soap can include, for example, from about0.1% to about 30%, by weight of the personal care composition, of water,from about 40% to about 99%, by weight of the personal care composition,of soap, and from about 0.25% to about 3%, by weight of the personalcare composition, of a particulate antimicrobial agent.

Bar soap compositions can be referred to as conventional solid (i.e.non-flowing) bar soap compositions. Some bar soap composition cancomprise convention soap, while others can contain syntheticsurfactants, and still others can contain a mix of soap and syntheticsurfactant. Bar compositions can include, for example, from about 0% toabout 45% of a synthetic anionic surfactant. An example of a suitableconventional soap can include milled toilet bars that are unbuilt (i.e.include about 5% or less of a water-soluble surfactancy builder).

A personal care bar composition can include soap. By weight, the soapcan be, for example, from about 45% to about 99%, or from about 50% toabout 75%, by weight of the personal care composition. Such soaps caninclude a typical soap, i.e., an alkali metal or alkanol ammonium saltof an alkane- or alkene monocarboxylic acid. Sodium, magnesium,potassium, calcium, mono-, di- and tri-ethanol ammonium cations, orcombinations thereof, can be suitable for a personal care composition.The soap included in a personal care composition can include sodiumsoaps or a combination of sodium soaps with from about 1% to about 25%ammonium, potassium, magnesium, calcium, or a mixture of these soaps.Additionally, the soap can be well-known alkali metal salts of alkanoicor alkenoic acids having from about 12 to about 22 carbon atoms or fromabout 12 to about 18 carbon atoms. Another suitable soap can be alkalimetal carboxylates of alkyl or alkene hydrocarbons having from about 12to about 22 carbon atoms. Additional suitable soap compositions aredescribed in U.S. Pre-Grant Publication No. 2012/0219610 A1.

A personal care composition can also include soaps having a fatty acid.For example, one bar soap composition could contain from about 40% toabout 95% of a soluble alkali metal soap of C₈-C₂₄ or C₁₀-C₂₀ fattyacids. The fatty acid can, for example, have a distribution of coconutoil that can provide a lower end of a broad molecular weight range orcan have a fatty acid distribution of peanut or rapeseed oil, or theirhydrogenated derivatives, which can provide an upper end of the broadmolecular weight range. Other such compositions can include a fatty aciddistribution of tallow and/or vegetable oil. The tallow can includefatty acid mixtures that can typically have an approximate carbon chainlength distribution of 2.5% C₁₄, 29% C₁₆, 23% C₁₈, 2% palmitoleic, 41.5%oleic, and 3% linoleic. The tallow can also include other mixtures witha similar distribution, such as fatty acids derived from various animaltallows and/or lard. In one example, the tallow can also be hardened(i.e., hydrogenated) such that some or all unsaturated fatty acidmoieties can be converted to saturated fatty acid moieties.

Suitable examples of vegetable oil include palm oil, coconut oil, palmkernel oil, palm oil stearine, soybean oil, and hydrogenated rice branoil, or mixtures thereof, since such oils can be among more readilyavailable fats. One example of a suitable coconut oil can include aproportion of fatty acids having at least 12 carbon atoms of about 85%.Such a proportion can be greater when mixtures of coconut oil and fatssuch as tallow, palm oil, or non-tropical nut oils or fats can be usedwhere principle chain lengths can be C₁₆ and higher. The soap includedin a personal care composition can be, for example, a sodium soap havinga mixture of about 67-68% tallow, about 16-17% coconut oil, about 2%glycerin, and about 14% water.

Soap included in a personal care composition can also be unsaturated inaccordance with commercially acceptable standards. For example, a soapincluded in a personal care composition can include from about 37% toabout 45% unsaturated saponified material.

Soaps included in a personal care composition can be made, for example,by a classic kettle boiling process or modern continuous soapmanufacturing processes wherein natural fats and oils such as tallow orcoconut oil or their equivalents can be saponified with an alkali metalhydroxide using procedures well known to those skilled in the art. Soapcan also be made by neutralizing fatty acids such as lauric (C₁₂),myristic (C₁₄), palmitic (C₁₆), or stearic (C₁₈) acids, with an alkalimetal hydroxide or carbonate.

Soap included in a personal care composition could also be made by acontinuous soap manufacturing process. The soap could be processed intosoap noodles via a vacuum flash drying process. One example of asuitable soap noodle comprises about 67.2% tallow soap, about 16.8%coconut soap, about 2% glycerin, and about 14% water, by weight of thesoap noodle. The soap noodles can then be utilized in a milling processto finalize a personal care composition.

Test Methods for the Commercial Products/Formulations

Viscosity Test Method

Viscosity is measured using an AR 550 rheometer/viscometer from TAinstruments (New Castle, Del., USA), using parallel steel plates of 40mm diameter and a gap size of 500 μm. The high shear viscosity at 20 isobtained from a logarithmic shear rate sweep from 0.1 s⁻¹ to 25 s⁻¹ in 3minutes time at 21° C.

Test Method for Determining the Logarithm of the Octanol/Water PartitionCoefficient (Log P)

The value of the log of the Octanol/Water Partition Coefficient (log P)is computed for each PRM in the perfume mixture being tested. The log Pof an individual PRM is calculated using the Consensus log PComputational Model, version 14.02 (Linux) available from AdvancedChemistry Development Inc. (ACD/Labs) (Toronto, Canada) to provide theunitless log P value. The ACD/Labs' Consensus log P Computational Modelis part of the ACD/Labs model suite.

Cleaning and/or Treatment Composition Examples

A series of cleaning and/or treatment compositions are prepared andevaluated as follows: the examples being designated with the letters CLfollowed by the sequence to distinguish from the microcapsule examples,noted above. In each example and table below, the amounts of eachingredient is presented as a wt %.

Example CL1—Light Cleaning/Additive Composition

A liquid composition for very light cleaning or additive to the laundryprocess is prepared with microcapsules of the present invention bycombining the microcapsules with the additional ingredients presented inTable 9.

TABLE 9 Ingredients Amount Nonionic Surfactant (1) 0-10 Emulsifier (2)0-10 Cationic surfactant 0-10 Anti-bac 0-5 Free (Neat) Perfume 0-10Microcapsules (3) 0-10 Structurant 0-0.3 Aesthetics Dye 0.015 WaterBalance (1) Alkyl ethoxylate with alkyl chain length between C8 and C18,preferably C12 to C16 and mixtures thereof with 3 to 12 ethoxylategroups, preferably 5 to 9. (2) Emulsifier description, includingCremophor, Basophor, Spans and Tweens, etc. (3) Microcapsules made inaccordance with the examples of the present specification

Example CL 2—Liquid Detergent Compositions

A HDL-Heavy Duty Liquid composition is prepared with microcapsules ofthe present invention by combining the microcapsules with the additionalingredients presented in Table 10. The exemplified space is meant torepresent dilute to concentrated detergent products. The resultingdetergent liquid product when used to wash articles of clothing iseffective at freshening washed clothing.

TABLE 10 Ingredient % wt Active Alkyl (ethoxy) sulfate (1)  0-30 Linearalkyl benzene sulfonic acid (2)  0-30 HSAS (3)  0-30 Nonionic Surfactant(4)  0-15 Amine Oxide 0-8 Citric Acid  0-10 Lactic Acid  0-10 C₁₂-C₁₈Fatty Acid 0-5 Protease (55.3 mg/g) 0-3 Amylase (25.4 mg/g) 0-2 Borax0-5 Calcium Formate   0-0.5 Polyethyleneimine 600, EO20 (5) 0-5Polyethyleneimine 600, EO24, PO16 (6) 0-5 DTPA (7) 0-5 OpticalBrightener (8) 0-1 NaOH As needed Na Cumene Sulfonate 0-5 Na Formate 0-1MEA hydrogenated castor oil   0-0.5 Aesthetics Dye   0-1.0 Free (Neat)Perfume   0-3.0 Microcapsules (9) 0-5 Water and Solvent To 100 pH3.5-8.5 (1) Typically the alkyl group has about 12 to about 18 carbonsand with 0 to about 3 ethoxylate groups. (2) Typically the alkyl grouphas about 10 to about 16 carbons. (3) HSAS is secondary alkyl sulfate,acid form (4) Alkyl ethoxylate with about 12 to about 18 carbons andabout 5 to about 9 moles ethoxylation. (5) Polyethyleneimine at about600 molecular weight reacted with about 20 moles of ethylene oxide. (6)Polyethyleneimine at about 600 molecular weight reacted with about 24moles of ethylene oxide and about 16 moles of propylene oxide. (7)Select optical brighteners from one or more of the following, Brightener14, Brightener 36, Brightener 49. (8) Select chelant from one or acombination of the following non-limiting list DTPA is diethylenetriamine pentaacetic acid, Tiron ® is4,5-Dihydroxy-1,3-benzenedisulfonic acid disodium salt monohydrate, EDTAethylene diamine tetra acetate, HEDP1-Hydroxyethylidene-1,1-diphosphonic Acid, Octapirox1-Hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridoneEthanolamine, EDDS Ethylenediamine-N,N′-disuccinic acid. (9)Microcapsules made in accordance with the examples of the presentspecification

Example CL3—Liquid Fabric Enhancer Composition

Examples of liquid fabric enhancer compositions are prepared withmicrocapsules of the present invention by combining the microcapsules ofthe present invention with the additional ingredients as presented inTable 11.

TABLE 11 Ingredient A B C D FSA¹ 12 21 18 14 Low MW alcohol 1.95 3.0 3.02.28 Structurant 1.25² NIL 0.2³ NIL Free (Neat) Perfume 1.50 1.8 2.01.50 Microcapsules⁴ 4.0 1.85 1.85 3.7 Calcium Chloride 0.10 0.12 0.10.45 DTPA⁶ 0.005 0.005 0.005 0.005 Preservative (ppm)⁷ 5 5 5 5 Antifoam⁸0.015 0.15 0.11 0.011 Polyethylene imines⁹ 0.15 0.05 NIL 0.1 PDMSemulsion¹⁰ NIL 0.5 1 2.0 Dispersant¹¹ NIL NIL 0.5 0.2 Organosiloxane¹² 5NIL NIL NIL Front-end Stability Aid 0.06¹³ 0.63¹⁴ 0.36¹³ 0.14¹⁴ Dye(parts per million ppm) 40 11 30 40 Ammonium Chloride 0-0.1 0-0.1 0-0.10.10 Hydrochloric Acid 0.010 0.01 0.10 0.010 Water Balance BalanceBalance Balance ¹N,N-di(tallowoyloxyethyl)-N,N-dimethylammoniumchloride. ²Cationic high amylose maize starch-available from NationalStarch under the trade name HYLON VII ®. ³Cationic polymer availablefrom BASF ® under the name Rheovis ® CDE. ⁴Microcapsules made inaccordance with the examples of the present specification ⁵Diethylenetriamine pentaacetic acid ⁶19% active aqueous solution of 1,2Benzisothiazolin-3-one (BIT) in dipropylene glycol and water availablefrom Dow Chemical under the trade name Koralone B-119 ⁷Silicone antifoamagent available from Dow Corning ® under the trade name DC2310.⁸Polyethylene imines available from BASF under the trade name Lupasol ®.⁹Polydimethylsiloxane emulsion from Dow Corning ® under the trade nameDC346. ¹⁰Non-ionic such as TWEEN 20 ™ or cationic surfactant as Berol648 and Ethoquad ® C 25 from Akzo Nobel. ¹¹Organosiloxane polymercondensate made by reacting hexamethylenediisocyanate (HDI), and a, wsilicone diol and 1,3-propanediamine,N′-(3-(dimethylamino)propyl)-N,N-dimethyl-Jeffcat Z130) orN-(3-dimethylaminopropyl)-N,Ndiisopropanolamine (Jeffcat ZR50)commercially available from Wacker Silicones, Munich, Germany.¹²Fineoxocol ® 180 from Nissan Chemical Co. ¹³Isofol ® 16 from Sasol.**For example PGE

Liquid fabric enhancer compositions in EXAMPLE CL3 are made by combiningthe molten fabric softener active with the front-end stability agent toform a first mixture. This first mixture is combined with water andhydrochloric acid using a high shear mixing device to form a secondmixture. The adjunct ingredients are combined with the second mixtureusing low shear mixing to form the fabric enhancing formula.

Liquid fabric enhancer compositions in EXAMPLE CL3 are used by dosing 10to 60 g of the formula into the rinse liquor for example via dispensinginto a clothes washing machine. Clothes are dried on a line or in anautomated clothes dryer. The fabrics treated with these formulas haveimproved feel and scent.

Example CL4—Liquid Fabric Enhancer Composition

Examples of liquid fabric enhancer compositions are prepared withmicrocapsules of the present invention by combining the microcapsuleswith the additional ingredients as presented in Table 12.

TABLE 12 Ingredients A B C D E F G H I DEEDMAC¹ 16 9 9 12 4 NIL NIL NILNIL Dialkyl esterdimethyl NIL NIL NIL NIL NIL 7 2.5 9 11 ammonium methylsulfate² HCl 0.02 0.01 0.01 0.01 NIL 0.01 NIL 0.01 0.01 Fromic Acid 0.050.05 0.05 0.05 0.05 0.05 0.025 0.05 0.05 Proxel ®³ 0.02 0.02 0.02 0.020.02 0.02 0.02 0.02 0.02 CaCl2 1 0.3 0.3 0.4 NIL 0.3 NIL 0.1 0.1Antifoam MP10⁴ 0.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Rheovis CDE ®⁵ 0.1NIL NIL NIL 0.4 0.1 0.2 NIL 0.2 Flosoft ®⁶ NIL 0.1 0.1 0.05 NIL NIL NIL0.3 NIL Bardac 2250 ®⁷ NIL NIL 0.5 NIL NIL NIL NIL NIL 0.5 NaHEDP⁸ 0.030.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Genapol T680 ®⁹ NIL NIL NIL NILNIL NIL NIL 0.6 0.8 CAE10¹⁰ NIL 0.6 NIL NIL NIL NIL NIL NIL NIL GlycerolNIL 10 NIL NIL NIL NIL NIL NIL 5 Perfume 0-2   0-1   0-1.5 0-3 0-2.30-1.5 0-3   0-0.8 0-0.5 Encapsulated 0-0.25 0-0.5 0-1   0-0.6 0-1.50-3   0-0.5 0-1   0-5   perfume Water To 100 To 100 To 100 To 100 To 100To 100 To 100 To 100 To 100 ¹91% activity, 9% isopropanol, supplied byEvonik ²Reaction product of triethanolamine and alkyl and/or fatty acidsfollowed by methylation. ³Proxel GXL, 20% activity, supplied by Lonza⁴MP10, 8% activity, supplied by Dow Corning ⁵Rheovis CDE, supplied byBASF ⁶Flosoft 222, supplied by SNF ⁷Bardac 2250, 50% activity, suppliedby Lonza ⁸20% activity ⁹Genapol T680, supplied by Clariant ¹⁰C12-14ALCOHOL ETHOXYLATE AE 10 (24E10)

Example CL5—Soluble Uni-Dose Heavy Duty Liquid Composition

Examples of Soluble Uni-dose heavy duty liquid composition are preparedwith microcapsules of the present invention by combining themicrocapsules with the additional ingredients as presented in Table 13.The resulting Unidose pouch product when used to wash articles ofclothing is effective at freshening garments.

TABLE 13 F 3 compartments A B C D E pouched product Form liquid liquidliquid liquid gel liq liq liq Compartment # 1 1 1 1 1 1 2 3 Dosage (g)36.0 38.0 32.0 36.0 40.0 34.0 25 35 Alkylbenzene sulfonic 14.5 13.8 16.014.5 13.5 14.5 20.0 NIL acid C₁₂₋₁₄ alkyl ethoxy 3 8.5 16.4 10.0 8.515.0 8.5 NIL NIL sulfate C₁₂₋₁₃ alkyl 3- NIL NIL NIL 13.0 NIL NIL NILNIL ethoxylate C₁₂₋₁₄ alkyl 7- 12.5 9.0 14.0 NIL 4.0 12.5 17.0 NILethoxylate C12-18 Fatty acid 14.5 8.5 16.0 15.0 7.2 14.5 13.0 NIL Citricacid NIL NIL NIL 2.0 4.1 NIL NIL NIL Enzymes 0-3 0-3 0-3 NIL 0-3 0-3 0-3NIL PAP granule¹ NIL NIL NIL NIL NIL NIL NIL 50.0 Ethoxysulfated NIL 3.0NIL NIL NIL NIL 2.2 NIL Hexamethylene Diamine Dimethyl Quat Ethoxylated4.0 1.0 NIL 4.0 3.0 2.0 NIL NIL Polyethylenimine Hydroxyethane 1.0 1.0NIL NIL 1.6 0.6 0.6 NIL diphosphonic acid Ethylene diamine NIL NIL NIL1.0 NIL NIL NIL NIL tetra(methylene phosphonic) acid Brightener 0.2 0.20.3 0.3 0.2 0.2 0.2 NIL Polydimethyl Siloxane NIL NIL 3.0 NIL NIL NILNIL NIL Hueing dye² NIL NIL NIL NIL NIL NIL 0.05 NIL Perfume   0-3.0  0-3.0   0-3.0   0-3.0   0-3.0   0-3.0 NIL NIL Microcapsules of the 0-50-5 0-5 0-5 0-5 0-5 NIL NIL present invention Water and minors To 100%Buffers (sodium To pH 8.0 carbonate, monoethanolamine) Solvents (1,2 To100% propanediol, ethanol), Sulfate ¹ε-Phthalimido-peroxy-hexanoic acidparticles made by Solvay Chemicals International, Brussels, Belgium.

Example CL 6—Dish Cleaning Composition

Examples of Dish cleaning compositions are prepared with microcapsulesof the present invention by combining the microcapsules with theadditional ingredients presented in Table 14.

TABLE 14 EXAMPLES A B C D E F G Alkyl C₁₀₋₁₄ Ethoxy Sulphate (AE0.6S)26.9  NIL NIL 25.7  NIL 11.1  21.0  Alkyl C₁₀₋₁₄ Ethoxy Sulphate (AE2S)NIL 18.7  26.9  NIL 18.7  NIL NIL Sodium alkyl benzene sulfonate NIL 8.0NIL NIL NIL NIL NIL Sodium paraffin sulfonate NIL NIL NIL NIL 8.0 NILNIL C12-14 dimethyl amine oxide 6.1 NIL NIL 4.1 NIL 3.7 10.0  Cocamidopropyl betaine NIL 4.5 6.8 3.2 6.0 NIL NIL C12-13 EO7 nonionic NIL NILNIL NIL NIL 1.0 2.0 Branched Nonionic: 3-propyl heptanol 1.0 0.8 NIL NILNIL NIL 1.0 EO8 PEI600-EO10-PO7 block polymer NIL NIL 0.8 NIL NIL 0.40.8 Perfume 0-2 0-2 0-2 0-2 0-2 0-2 0-2 Perfume microcapsule of thepresent 0-1   0-0.5   0-0.5   0-1.5   0-0.5   0-0.8 0-2 inventionEthanol 4.0 5.0 3.0 3.0 2.0 NIL 3.0 Polypropylene glycol MW2000 1.1 0.81.1 1.1 1.1 0.5 1.1 Sodium Chloride 1.3 0.8 1.3 0.5 0.8 1.3 1.3 Minors*and water to balance up to 100%

Example CL7—Compositions for Use in Cleaning in an Automatic DishwashingMachine

Automatic dish washing compositions are prepared with microcapsules ofthe present invention by combining the microcapsules with the additionalingredients presented in Table 15. Some aspects of the present inventionhave at least one water soluble compartment, preferably composed ofMonosol 660 mm M8630K Water Soluble Film. In other aspects of thepresent invention the unit dose composition has more than onecompartment and at least one of the compartments comprises powder as inEXAMPLE CL7 A.

TABLE 15 % wt Active A B C Ingredients POWDER LIQUID LIQUID Sodiumsulfate  0-15 2-7 NIL Soda ash 20-50 NIL NIL Zinc carbonate NIL 0.1-0.2NIL Zinc sulfate NIL NIL 0.3-0.7 Sodium silicate 0-2  3-15 1-2 Sodiumbicarbonate NIL NIL 15-25 Glutamic acid-N,N-diacetic acid, NIL NIL 3-7tetra sodium salt. Citric acid NIL NIL 1-2 NaOH (preferably low iron)NIL   0-1.5 Carboxylate polymer, GT101 2.5-7   NIL 1.25 Plurafac SLF 1800.2-1.5 NIL 0.25-0.6  MDGA  5-15 NIL NIL Polyacrylate thickener PolygelNIL 0.7-2.3 NIL DKP Acrylic/sulfonic dispersant Acusol  2-10 NIL NIL 588Acrylic acid polymer Acusol NIL 1-3 NIL 425 N Sodium hypochlorite bleach 0-30 0.3-1.5 NIL Ultimase 0-2 NIL NIL Stainzyme 0-1 NIL NIL SavinaseUltra 16XL NIL NIL 0.2-0.5 Termamyl Ultra 300 L NIL NIL  0.1-0.15Calcium Chloride NIL NIL 0.3-0.4 Dipropylene Glycol NIL NIL NIL NonionicSurfactant NIL  9-50 NIL Plurafac SLF 180 NIL 25-60 NIL Glycerine NIL0-1 NIL Dye NIL   0-0.1 NIL Nitric acid NIL 0.005-0.05  NIL Preservativesodium benzoate NIL 0.25-0. 8 0.2-0.8 Perfume 0-1 0-1 0-1 Microcapsulesof the present 0-2 0-2 0-2 invention Balance Water To 100 To 100 To 100Fatty acid has C12 to C14 alkyl groups and mixtures thereof Rheovis ® AT120 is a methacrylate/acrylic acid copolymer.

Example CL8—Spray for Cleaning Hard Surfaces

A spray for cleaning hard surfaces is prepared with microcapsules of thepresent invention by combining the microcapsules with the additionalingredients presented in Table 16.

TABLE 16 Ingredients % wt Active C₁₃₋₁₅ alkyl ethoxylate (30) 0-0.5C₉₋₁₁ alkyl ethoxylate (8) 0-0.5 C_(12/14) Amine-oxide 0-3 Barquat4280-Z 0-3 Ethylene glycol monohexyl ether 0-1 Phenoxyethanol 0-1 DenseSoda ash 0-0.3 Pentasodum diethylene triamine (DTPA) 0-0.4 Tartaric acid0-0.1 Dye 0-1.2 1,2-Benzisothioazolin-3-one 0-0.1 Perfume 0-1Microcapsules of the present invention 0-0.5 Balance Water To 100

Solid Consumer Products Examples Example CL9—Free Flowing Particles

Free flowing particles are prepared with microcapsules of the presentinvention by combining the microcapsules with the additional ingredientspresented in Table 17.

TABLE 17 % wt Active Ingredients A B C D Polyethylene 70-99  0-20 0-290-40 glycol Clay 0-29 0-20 0-20 0-10 NaCl 0-29 50-99  0-29 0-40 Na2SO40-10 0-10 0-10 0-5  Urea 0-29 0-29 0-99 0-40 Polysaccharide 0-29 0-290-29 0-5  Zeolite 0-29 0-29 0-29 0-5  Plasticizers/ SolventsStarch/Zeolite 0-29 0-29 0-29 0-5  Silica 0-5  0-5  0-5  0-5  Metaloxide 0-29 0-29 0-29 0-29 Metal catalyst 0.001-0.5   0.001-0.5  0.001-0.5   0.001-0.5   Opacifier 0-5  0-5  0-1  0-1  Water 0-2  0-2 0-5  0-5  Perfume 0-5  0-5  0-5  0-5  Microcapsules 0-10  0-4.5 0-3  0-7.5 made in accordance with the examples of the present specification

Example CL10—Spray-Dried Laundry Detergent Powder Composition

Spray-Dried Laundry Detergent Powder compositions are prepared withmicrocapsules of the present invention by combining the microcapsuleswith the additional ingredients as presented in Table 18

TABLE 18 Ingredients wt % Active Slurry A B C D Linear alkyl benzenesulfonate 10.6 15.8 21.3 35.7 Acrylate/maleate copolymer 4.6 6.8 9.414.2 Ethylenediame disuccinic acid and/ 1.4 2.1 1.7 2.9 or Hydroxyethanedimethylene phosphonic acid Sodium carbonate 19.4 26.5 18.8 29.9 Sodiumsulfate 28.6 42.4 — — Carboxy methyl cellulose polymer — — 4.3 7.1Carboxy methyl cellulose polymer — — 4.3 7.1 Miscellaneous, such asmagnesium 1.4 2.2 2.5 4.2 sulfate, brightener and one or morestabilizers Perfume 0-3 0-2 0-2 0-3 Microcapsules made in accordance 0-50-5 0-5 0-5 with the examples of the present specification Water BalanceBalance Balance Balance

A first spray-dried laundry detergent powder is formed from an aqueousslurry, slurry A from Table 18, which is prepared having a moisturecontent of 34.0%. Any ingredient added above in liquid form is heated to70° C., such that the aqueous slurry is never at a temperature below 70°C. At the end of preparation, the aqueous slurry is heated to 80° C. andpumped under pressure (5×10⁶ Nm⁻²) into a counter current spray-dryingtower with an air inlet temperature of from 290° C. The aqueous slurryis atomized and the atomized slurry is dried to produce a solid mixture,which is then cooled and sieved to remove oversize material (>1.8 mm) toform a spray-dried powder, which is free-flowing. Fine material (<0.15mm) is elutriated with the exhaust the exhaust air in the spray-dryingtower and collected in a post tower containment system. The spray-driedpowder has a moisture content of 2.0 wt %, a bulk density of 310 g/l anda particle size distribution such that greater than 90 wt % of thespray-dried powder has a particle size of from 150 to 710 micrometers.The composition of the spray-dried powder A is listed in the Table 18.Perfume and microcapsules are sprayed onto the composition following thespray dry procedure.

A second spray-dried laundry detergent powder is formed from an aqueousslurry, slurry B from Table 18, having a moisture content of 42.0%. Anyingredient added above in liquid form is heated to 70° C., such that theaqueous slurry is never at a temperature below 70° C. At the end ofpreparation, the aqueous slurry is heated to 85° C. and pumped underpressure (from 6.5×10⁶ Nm⁻²), into a counter current spray-drying towerwith an air inlet temperature of from 275° C. The aqueous slurry isatomized and the atomized slurry is dried to produce a solid mixture,which is then cooled and sieved to remove oversize material (>1.8 mm) toform a spray-dried powder B, which is free-flowing. Fine material (<0.15mm) is elutriated with the exhaust the exhaust air in the spray-dryingtower and collected in a post tower containment system. The spray-driedpowder has a moisture content of 3.0 wt %, a bulk density of 250 g/l anda particle size distribution such that greater than 90 wt % of thespray-dried powder has a particle size of from 150 to 710 micrometers.The composition of the spray-dried powder is given in Table 18. Perfumeand microcapsules are sprayed onto the composition after the spray dryprocess.

Example CL11—Freshening Composition

Liquid fabric spray fabric freshening compositions are prepared withmicrocapsules of the present invention by combining the microcapsuleswith the additional ingredients as presented in Table 19. The resultingfabric refreshing spray product when used to treat fabric surfaces iseffective at freshening a treated fabric.

TABLE 19 wt % Active Ingredient A B C D E Deionized Water BalanceBalance Balance Balance Balance Ethanol 3.0 3.0 3.0 3.0 3.0 Lupasol HF¹NIL NIL NIL NIL NIL Hydroxypropyl b-CD NIL NIL NIL NIL NIL DiethyleneGlycol NIL NIL NIL NIL NIL Silwet L-7600 0.1 0.1 0.1 0.100 0.100Basophor EL60² NIL 0.05 0.05 0.05 0.05 Maleic Acid and/or Citric Acid³As As needed As needed As needed As needed needed Koralone B-119 0.0150.015 0.015 0.015 0.015 Hydroxypropyl β-cyclodextrin NIL NIL NIL NIL NILSodium Hydroxide³ As As needed As needed As needed As needed neededMicrocapsules made in 1 2 0.1 5 0.05 accordance with the examples of thepresent specification Fragrance 0 0 0 0 0 Target pH 6.8 6.8 6.8 6.8 6.8Total 100 100 100 100 100

Example CL12—Dryer Added Fabric Softener Sheet Composition

A series of dryer added fabric softener sheet compositions are preparedwith microcapsules of the present invention by combining themicrocapsules with the additional ingredients as presented in Table 20.The compositions A-D of this example are mixed homogeneously andimpregnated onto a non-woven polyester sheet having dimensions of about6% in×12″ (about 17.1 cm×30.5 cm) and weighing about 1 gram. Theresulting dryer added fabric softener sheet product when added to anautomatic dryer is effective at softening, freshening and reducing thestatic on clothing that contact the sheet.

TABLE 20 A Wt % B C D Ingredient Active Wt % Active Wt % Active Wt %Active DEQA¹ 0-50 50 — — DEQA² 0-50 — — 30 DTDMAMS³ 0-50 — 50 — 7018FA⁴0-50 — 50 — TS-20⁵ 0-15 — — 15 SMS⁶ 0-15 — — 15 SDASA⁷ 0-19 25 — 19TPED⁸ —  3 — — Complex⁹   0-16.5   16.5 —   8.0 Clay¹⁰ Balance BalanceBalance Balance Free (Neat) Perfume 0-4  0-1.5 0-3   0-1.5Microcapsules¹¹ 0-4  0-4   0-2 0-2 Active Weight 2.4   2.4   1.9   2.4(g/sheet) ¹DEQA¹: Di(soft tallowoyloxyethyl)dimethylammonium methylsulfate with 25%> 7018 FA, as described below, as solvent ²DEQA²:Di(soft tallowoyloxyethyl)hydroxyethylmethylammoniun methyl sulfate with18% 

 partially hydrogenated tallow fatty acid solvent ³DTDMAMS:Di(hydrogenated tallowalkyl)dimethylammonium methyl sulfate ⁴7018FA:70:30 Stearic Acid:Palmitic Acid (IV = 0) Industrene 7018 sold by Witco⁵TS-20: Polyoxyethylene-20 Sorbitan Tristearate (Glycosperse TS-20, soldby Lonza ⁶SMS: Sorbitan Mono Stearate ⁷SDASA: 1:2 ratio of stearyldimethyl amine:triple pressed stearic acid ⁸TPED:N,N,N′,N′-Tetrakis(2-hydroxypropyl)ethylenediamine (Quadrol, sold byBASF) ⁹Complex: Beta-Cyclodextrin/Perfume Complex ¹⁰Clay: CalciumBentonite Clay (Bentonite L sold by Southern Clay Products Free (Neat)Perfume ¹¹Microcapsules made in accordance with the examples of thepresent specification

Examples CL13-CL15—Absorbent Articles Example CL13—Pads for MenstrualOdor Control

The microcapsules of the present invention are added into the core of anAlways Ultra Thin Unscented menstrual pad. Optionally, a neat fragranceis preferably added beneath the core of the article.

Example CL14—Heavy Al Pants for Urine Odor Control

The microcapsules of the present invention are added into the core of anAlways Discreet Adult Incontinence Underwear, moderate absorbency.Optionally, a neat fragrance is preferably added beneath the core of thearticle.

Example CL15—Diapers for Odor Control

The microcapsules of the present invention are added into the core of anPampers Cruisers Baby Diaper. Optionally, a neat fragrance is preferablyadded beneath the core of the article.

Examples CL16-CL17—Personal Care Compositions Example CL16—Body Wash

Body Wash compositions are prepared with microcapsules of the presentinvention by combining the microcapsules with the additional ingredientsas presented in Table 21.

TABLE 21 Body Wash A B C Sodium Laureth-3 Sulfate (as 28% active) 27.85%27.85% 27.85% Water Q.S. Q.S. Q.S. Sodium Lauryl Sulfate (as 29% active)10.34 10.34 10.34 Cocamidopropyl Betaine B (30% active) 4.01 4.01 4.01Citric Acid 0.18 0.18 0.18 Sodium Benzoate 0.3 0.3 0.3 Disodium EDTA0.12 0.12 0.12 Methylchloroisothiazolinone/ 0.04 0.04 0.04Methylisothiazolinone Sodium Chloride 2.35 1.7 1.6 Neat Perfume 1.25 1 2Microcapsules made in accordance with the 0.25 0.175 0.25 examples ofthe present specification QS - indicates that this material is used tobring the total to 100%

Example CL17—Shampoos

Shampoo compositions are prepared with microcapsules of the presentinvention by combining the microcapsules with the additional ingredientsas presented in Table 22.

TABLE 22 A B C Ingredient Wt % D E F Ammonium Laureth Sulfate¹ 14.1 14.114.1 14.1 14.1 14.1 Ammonium Lauryl Sulfate² 3.1 3.1 3.1 3.1 3.1 3.1Ammonium Xylenesulfonate³ 0.45 0.45 0.45 0.45 0.45 0.45 TWEEN 60⁴ 3.03.0 3.0 3.0 3.0 3.0 Polyquaternium-10⁵ 0.35 0.35 0.35 0.35 0.35 0.35Cetrimonium Chloride⁶ 0.5 0.5 0.5 0.5 0.5 0.5 Selenium Sulfide⁷ 1.0 1.01.0 1.0 0.2 0.2 Dimethicone⁸ 0.60 0.60 0.60 0.60 0.60 0.60 EthyleneGlycol Distearate⁹ 3.0 3.0 3.0 3.0 3.0 3.0 Cocamide MEA¹⁰ 3.0 3.0 3.03.0 3.0 3.0 Zinc Pyrithione¹¹ — 0.2 0.2 — 1.0 1.0 Zinc Carbonate¹² — —1.61 — — 1.61 Neat Fragrance 1.1 0.75 0.75 0.65 0.85 1.0 Microcapsulesmade in 0.25 0.25 0.175 0.175 0.175 0.175 accordance with the examplesof the present specification Cetyl Alcohol¹³ 0.42 0.42 0.42 0.42 0.420.42 DMDM Hydantoin 0.40 0.40 0.40 0.40 0.40 0.40 Sodium Chloride 0.300.30 0.30 0.30 0.30 0.30 Stearyl Alcohol¹⁴ 0.20 0.20 0.20 0.20 0.20 0.20Hydroxypropyl Methylcellulose¹⁵ 0.02 0.02 0.02 0.02 0.02 0.02 Water Q.S.Q.S. Q.S. Q.S. Q.S. Q.S. ¹Ammonium Laureth Sulfate at 25% active,supplier: P&G ²Ammonium Lauryl Sulfate at 25% active, supplier: P&G³Ammonium Xylene Sulfonate 40% active, supplier: Stepan ⁴Polysorbate 60,upplier: Croda ⁵UCARE Polymer LR400, supplier - Dow Chemical⁶cetrimonium chloride, supplier - Croda ⁷Selenium disulfide, supplierEskay ⁸Viscasil 330M from Momentive Performance Materials with aviscosity of 330,000 cSt (centistokes). ⁹Ethylene Glycol Disterate,supplier: Stepan ¹⁰Ninol COMF from the Stepan Company ¹¹Zinc Pyrithione,supplier Lonza ¹²Zinc Carbonate Basic, supplier Pan Continental Chemical¹³Cetyl Alcohol, supplier P&G ¹⁴Stearyl Alcohol, supplier P&G¹⁵Methocel, supplier Dow Chemical

Examples CL18-CL20—Antiperspirant and/or Deodorant Compositions ExampleCL18—Deodorants

Deodorants are prepared with microcapsules of the present invention bycombining the microcapsules with the additional ingredients as presentedin Table 23.

TABLE 23 Ingredient A B C D E Product Form Solid Solid Solid SolidAerosol Deodorant Deodorant Deodorant Deodorant Deodorant or Body Spraydipropylene glycol 48 48 20 30 20 propylene glycol 19.3 19.3 22 — —tripopylene glycol — — 25 — — Glycerine — — — 10 — PEG-8 — — — 20 —Propylene Glycol 3 1.4 1.4 — — — Myristyl Ether ethanol — — — — QS WaterQS QS QS QS — sodium stearate 5.4 5.4 5.5 5.5 — tetra sodium EDTA 0.50.5 0.05 0.05 — sodium hydroxide — — 0.04 0.04 — triclosan — — 0.3 0.3 —Neat Perfume 2.8 2.8 2 1.5 1.5 Microcapsules made 3 0.7 1.0 0.5 0.35 inaccordance with the examples of the present specification Blue 1 0.00090.0009 — — — Propellant (1,1 — — — — 40 difluoroethane) QS - Indicatesthat this material is used to bring the total to 100%.

Example CL19—Antiperspirants

Antiperspirant compositions are prepared with microcapsules of thepresent invention by combining the microcapsules with the additionalingredients as presented in Table 24.

TABLE 24 Form Invisible Invisible Invisible Soft Soft Soft Solid SolidSolid Solid Solid Solid Ingredient A B C D E F Aluminum Zirconium 24 2424 26.5 26.5 26.5

chlorohydrex Glycine Powder Cyclopentasiloxane Q.S Q.S. Q.S. Q.S. Q.S.Q.S. Dimethicone — — — 5 5 5 CO-1897 Stearyl Alcohol NF 14 14 14 — — —Hydrogenated Castor Oil MP80 3.85 3.85 3.85 — — — Deodorized BehenylAlcohol 0.2 0.2 0.2 — — — Tribehenin — — — 4.5 4.5 4.5 C 18-36 acidtriglyceride — — — 1.125 1.125 1.125 C12-15 Alkyl Benzoate 9.5 9.5 5 — —— PPG-14 Butyl Ether 6.5 6.5 — 0.5 0.5 0.5 Phenyl Trimethicone 3 — 3 — —— White Petrolatum 3 — — 3 3 3 Mineral Oil 1.0 1.0 1.0 — — — Free (Neat)Perfume 1.0 0.75 2.0 0.75 1.0 1.25 Microcapsules made in accordance 0.253 0.35 0.175 0.25 0.1 with the examples of the present specificationBeta-Cyclodextrin complexed with — 3.0 — — — 3.0 Malodor reducingcomposition Talc Imperial 250 USP 3.0 3.0 3.0 — — — QS - indicates thatthis material is used to bring the total to 100%.

indicates data missing or illegible when filed

Example CL20—Clear Gel Antiperspirant

Clear gel antiperspirants are prepared with microcapsules of the presentinvention by combining the microcapsules with the additional ingredientsas presented in Table 25.

TABLE 25 3.1 3.2 3.3 3.4 3.5 Clear Gel Clear Gel Clear Gel Clear GelClear Gel Antiperspirant Antiperspirant Antiperspirant AntiperspirantAntiperspirant Aluminum Zirconium 20 18.5 20 18 10 Octachlorohydrex GlyWater Q.S Q.S. Q.S. Q.S. Q.S. Ethanol 5.5 8 6 6.5 5 Propylene Glycol 5.35 7 5.5 8 DC 5225c- 7.8 9 6.5 7 8 Cyclopentasiloxane & PEG/PPG-18/18Dimethicone Dimethicone 5.6 4.5 5.8 5 4.1 Cyclopentasiloxane 2.6 3 1 32.5 Free (Neat) Perfume 1.0 0.75 2.0 0.75 1.0 Microcapsules made 0.25 —0.35 0.175 0.25 in accordance with the examples of the presentspecification QS - indicates that this material is used to bring thetotal to 100%.

For avoidance of doubt and to preclude any unintentional omission of anembodiment, it is to be appreciated that the present teaching alsopertains to and by this reference incorporates any and all consumerproducts and methods of making consumer products containing or madeusing, respectively, the microcapsules embraced by the appended claimsas well as the microcapsules resulting from the methods of the appendedclaims in combination with at least one consumer product ingredient. Ingeneral, these compositions and methods will contain or employ, asappropriate, a sufficient amount of said microcapsules to provide, basedon the total consumer product weight, said consumer product with from0.001% about to about 25%, preferably from about 0.01% to about 10%,more preferably from about 0.05% to about 5%, most preferably from about0.1% to about 0.5% of said microcapsules.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests,or discloses any such invention. Further, to the extent that any meaningor definition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

Although the process and prepared microcapsules of the presentspecification as well as various commercial and consumer productscontaining/comprising the same have been described with respect tospecific embodiments and examples, it should be appreciated that thepresent teachings are not limited thereto and other embodimentsutilizing the concepts expressed herein are intended and contemplatedwithout departing from the scope of the present teaching as intended inthe true spirit and scope of the invention. It is therefore intended anyand all modifications, variations, or equivalents that fall within thespirit and scope of the underlying principles are within the scope ofthis invention and are covered by the appended claims.

1. Microcapsules whose shell wall comprises both melamine resin and(meth)acrylate polymer wherein the melamine resin is derived from afirst aqueous phase and the (meth)acrylate polymer is derived from asecond aqueous phase, said (meth)acrylate polymer comprising thereaction product of (a) at least one water soluble or dispersiblemultifunctional (meth)acrylate monomer or oligomer alone or incombination with (b) at least one water soluble or dispersible mono-and/or di-functional (meth)acrylate and/or (c) at least one watersoluble or dispersible simple base, wherein said shell wall is formed bythe sequential polymerization of the wall forming materials of the twoaqueous phases, one aqueous phase, either the first aqueous phase or thesecond aqueous phase, being subjected to wall forming conditions to forma first microcapsule wall before the other aqueous phase is subjected towall forming conditions to effect deposition and polymerization of thesecond wall forming material upon the first microcapsule wall.
 2. Themicrocapsules of claim 1 wherein the (meth)acrylate polymer comprisesthe reaction product of (a) at least one water soluble or dispersiblemultifunctional (meth)acrylate monomer or oligomer.
 3. The microcapsulesof claim 1 wherein the (meth)acrylate polymer comprises the reactionproduct of (a) at least one water soluble or dispersible multifunctional(meth)acrylate monomer or oligomer and (b) at least one water soluble ordispersible mono- and/or di-functional (meth)acrylate.
 4. Themicrocapsules of claim 1 wherein the (meth)acrylate polymer comprisesthe reaction product of (a) at least one water soluble or dispersiblemultifunctional (meth)acrylate monomer or oligomer and (c) at least onewater soluble or dispersible simple base.
 5. The microcapsules of claim1 wherein the (meth)acrylate polymer comprises the reaction product of(a) at least one water soluble or dispersible multifunctional(meth)acrylate monomer or oligomer, (b) at least one water soluble ordispersible mono- and/or di-functional (meth)acrylate, and (c) at leastone water soluble or dispersible simple base.
 6. The microcapsules ofclaim 1 wherein the (meth)acrylate polymer is derived from anoligomer/prepolymer formed by the reaction of (a) at least one watersoluble or dispersible multifunctional (meth)acrylate monomer oroligomer and (b) at least one water soluble or dispersible mono- and/ordi-functional (meth)acrylate.
 7. The microcapsules of claim 1 whereinthe (meth)acrylate polymer is derived from an oligomer/prepolymer formedby the reaction of (a) at least one water soluble or dispersiblemultifunctional (meth)acrylate monomer or oligomer and (c) least onewater soluble or dispersible simple base.
 8. The microcapsules of claim1 wherein the (meth)acrylate polymer is derived from anoligomer/prepolymer formed by the reaction of at least one water solubleor dispersible multifunctional (meth)acrylate monomer or oligomer, (b)at least one water soluble or dispersible mono- and/or di-functional(meth)acrylate and (c) at least one water soluble or dispersible simplebase.
 9. The microcapsules of claim 1 wherein the melamine resin isselected from a melamine-based polyurea, a melamine-formaldehyde resin,a melamine-aldehyde resin, dimethylol melamine urea, methylateddimethylol melamine urea, methylated melamine formaldehyde, methylatedmethylol melamine, and mixtures of melamine formaldehyde with ureaformaldehyde.
 10. The microcapsules of claim 1 wherein the melamineresin is derived from a melamine prepolymer that is formaldehyde freeand/or a methylated melamine resin.
 11. The microcapsules of claim 1wherein the melamine resin is a partially methylated or high iminomethylated melamine resin.
 12. The microcapsules of claim 1 wherein theshell wall of the microcapsule further comprises a polymeric emulsifieroriginating from the first aqueous phase which polymeric emulsifier isentrapped or encased in the shell wall material.
 13. The microcapsulesof claim 1 wherein the shell wall of the microcapsule further comprisesa polymeric emulsifier originating from the second aqueous phase whichpolymeric emulsifier is entrapped or encased in the shell wall material.14. The microcapsules of claim 1 wherein the shell wall of themicrocapsule further comprises a polymeric emulsifier originating fromboth the first aqueous phase and the second aqueous phase, whichpolymeric emulsifier is entrapped or encased in the shell wall material.15. The microcapsules of claim 1 wherein the shell wall comprises twodiscrete layers, a melamine resin layer and a (meth)acrylate polymerlayer, said shell wall having been formed by forming a microcapsuleusing either the first aqueous phase or the second aqueous phase,isolating the so formed microcapsules, placing them in the other aqueousphase and then subjecting the mixture to conditions to polymerize thewall forming material of that aqueous phase on the preformedmicrocapsules.
 16. The microcapsules of claim 15 wherein an interface ispresent between the two discrete layers said interface comprisingpolymer chains of the melamine resin and the (meth)acrylate polymerwhich are intertwined and/or embedded in the other.
 17. Themicrocapsules of claim 1 wherein the shell wall comprises an interiorsurface, an exterior surface and an intermediary section, wherein theinterior surface of the shell is wholly comprised of the wall formingmaterial of the first to be reacted of the two aqueous phases, theexterior surface is wholly comprised of wall forming material of thesecond to be reacted of the two aqueous phases, and an intermediarysection comprising an interpenetrating network and/or copolymer of thewall forming materials of the two aqueous phases.
 18. The microcapsulesof claim 17 wherein the shell wall was formed by forming a microcapsuleusing either the first aqueous phase or the second aqueous phase, whichmicrocapsule is impermeable to the wall forming material of the otheraqueous phase, then adding the other aqueous phase and then subjectingthe mixture to conditions to polymerize the wall forming material of theadded aqueous phase.
 19. The microcapsules of claim 18 wherein thepolymerization and wall formation of the first to be reacted aqueousphases completed or substantially completed prior to the addition of theother aqueous phase composition.
 20. The microcapsules of claim 17wherein the shell wall has been formed by sequentially polymerizing thewall forming materials of one phase before the other, the firstpolymerization being such that the monomer of the second to be reactedaqueous phase is unable to penetrate the shell wall formed of the firstto be reacted aqueous phase.